Additive for non-aqueous electrolyte solution, non-aqueous electrolyte solution, and non-aqueous electrolyte solution battery

ABSTRACT

An additive for a non-aqueous electrolyte solution that can exhibit high-temperature cycle properties at 50° C. or more and low-temperature output properties at −20° C. or less in a well-balanced manner for a non-aqueous electrolyte solution battery. The additive for a non-aqueous electrolyte solution is represented by formula [1],wherein Z1, Z2, Z3, Z4, Mp+ and p are as defined in the specification.

FIELD OF THE INVENTION

The present invention relates to an additive for a non-aqueouselectrolyte solution and a non-aqueous electrolyte solution that canimprove the low-temperature properties and the high-temperaturedurability in a well-balanced manner when used in a non-aqueouselectrolyte solution battery, as well as a non-aqueous electrolytesolution battery using the same.

BACKGROUND TECHNOLOGY

In recent years, storage systems to be applied to small equipment thatneeds high energy density, such as information-technology-relatedequipment or communication equipment, specifically, personal computers,video cameras, digital still cameras, and cell phones, and storagesystems to be applied to large equipment that needs high power, such asauxiliary power and energy storage for electric vehicles, hybridelectric vehicles and fuel cell electric vehicles have receivedattention. A non-aqueous electrolyte battery such as a lithium ionbattery, a lithium battery, a lithium ion capacitor or a sodium ionbattery has been actively developed as a candidate thereof.

Although many of these non-aqueous electrolyte solution batteries havealready been put into practical use, each property is not satisfactoryin various applications. In particular, in case of the use of beingmounted on a vehicle such as an electric vehicle, since highinput/output properties are required even in a cold season, theimprovement in low-temperature properties is important, andhigh-temperature cycle properties, such as maintenance of the properties(less increase in the internal resistance) even when repeatedly chargedand discharged in a high-temperature environment, are further required.

Until now, as a means of improving the high-temperature properties ofnon-aqueous electrolyte solution batteries and the battery properties(cycle properties) when charge and discharge are repeated, optimizationof various battery components including positive and negative electrodeactive materials has been studied. Non-aqueous electrolytesolution-related technology is also no exception, and it has beenproposed to use various additives for suppressing deterioration due todecomposition of the electrolyte solution on the surface of an activepositive electrode or negative electrode. For example, Patent Document 1proposes to improve battery properties by adding vinylene carbonate tothe electrolyte solution.

In addition, as disclosed in Patent Document 2, a method for improvingthe conductivity of cations (reducing resistance) by using the specificionic compound as a supporting electrolyte has been proposed.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: Japanese Patent Un-examined Publication number    (hereinafter referred to simply as JP-A number) JP-A-2000-123867-   Patent Document 2: JP-A-2001-507043

SUMMARY OF THE INVENTION Subject to be Attained by the Invention

In non-aqueous electrolyte solution batteries using non-aqueouselectrolyte solutions disclosed in the prior art documents, thecompatibility between the durability performance at high temperature andthe output performance at low temperature is not satisfactory, andaccordingly there was room for improvement.

For example, although an electrolyte solution containing vinylenecarbonate as disclosed in Patent Document 1 has improved cycleproperties at high temperature, it has a problem in that the internalresistance significantly increases and the low-temperature propertiesdecrease.

In addition, for example, although an electrolyte solution containing anionic compound as a supporting electrolyte as disclosed in Example 4 ofPatent Document 2 has improved cycle properties at high temperature, ithas a problem in that the effect of improving low-temperature propertiesis low.

Furthermore, an electrolyte solution containing an ionic compound as asupporting electrolyte as disclosed in disclosed in Example 15 of PatentDocument 2 has a problem in that the effects of improving the cycleproperties at high temperature and the low-temperature properties areboth low.

It is an object of the present invention to provide an additive for anon-aqueous electrolyte solution that can exhibit high-temperature cycleproperties at 50° C. or more and low-temperature output properties at−20° C. or less in a well-balanced manner, as well as a non-aqueouselectrolyte solution containing such an additive and a non-aqueouselectrolyte solution battery using such an electrolyte solution.

Means for Attaining the Subject of the Invention

The present inventors have intensively studied in view of the aboveproblems, and as a result, have found that when an ionic compound havingthe specific structure is used as an additive in a non-aqueouselectrolyte solution containing a non-aqueous solvent and a solute, anon-aqueous electrolyte solution battery using the resultant non-aqueouselectrolyte solution can exhibit high-temperature cycle properties andlow-temperature output properties in a well-balanced manner, and arrivedat the present invention.

That is, the present invention provides an additive for a non-aqueouselectrolyte solution (hereinafter, may be generally referred to simplyas “ionic compound”) represented by the following formula [1]:

In formula [1], Z¹ to Z⁴ are each independently a fluorine atom or anorganic group selected from the group consisting of linear or branchedalkyl groups having 1 to 10 carbon atoms, linear or branched alkoxygroups having 1 to 10 carbon atoms, linear or branched alkenyl groupshaving 2 to 10 carbon atoms, linear or branched alkenyloxy groups having2 to 10 carbon atoms, linear or branched alkynyl groups having 2 to 10carbon atoms, linear or branched alkynyloxy groups having 2 to 10 carbonatoms, cycloalkyl groups having 3 to 10 carbon atoms, cycloalkoxy groupshaving 3 to 10 carbon atoms, cycloalkenyl groups having 3 to 10 carbonatoms, cycloalkenyloxy groups having 3 to 10 carbon atoms, aryl groupshaving 6 to 10 carbon atoms, and aryloxy groups having 6 to 10 carbonatoms, where the organic group may contain a fluorine atom, an oxygenatom, or an unsaturated bond; and at least one of Z¹ to Z⁴ is a fluorineatom.

Incidentally, the phrase “the organic group contains a fluorine atom”specifically means that a hydrogen atom in the group is substituted witha fluorine atom.

In addition, the phrase “the organic group contains an oxygen atom”specifically means, for example, that “—O—” (ether bond) is interposedbetween the carbon atoms in the group.

M^(p+) is a proton, a metal cation, or an onium cation, and p is acation valence.

In the ionic compound, it is preferable that Z¹ and Z⁴ are independentlya fluorine atom or a group selected from the group consisting of amethyl group, a trifluoromethyl group, and a phenyl group; Z² and Z³ areeach independently a fluorine atom or a group selected from the groupconsisting of a methoxy group, an ethoxy group, a propoxyl group, anallyloxy group, a 2-propynyloxy group, and a phenyloxy group; and atleast one of Z² and Z³ is a fluorine atom.

In the ionic compound, M^(p+) is preferably a proton or at least onecation selected from the group consisting of a lithium ion, a sodiumion, a potassium ion, a tetraalkylammonium ion, and atetraalkylphosphonium ion.

In addition, the present invention relates to a non-aqueous electrolytesolution containing a non-aqueous solvent, a solute, and theabove-described additive for a non-aqueous electrolyte solution(hereinafter, may be referred to simply as “non-aqueous electrolytesolution” or “electrolyte solution”).

The content of the additive for a non-aqueous electrolyte solution ispreferably within a range of 0.005 to 5.0 mass % based on the totalamount of the non-aqueous solvent, the solute, and the additive for anon-aqueous electrolyte solution. If the content is higher than 5.0 mass%, the discharge capacity may be decreased by excessive formation of afilm. In contrast, if the content is less than 0.005 mass %, theformation of a film is insufficient, and the effect of improving theproperties may become difficult to be realized.

The solute is preferably at least one selected from the group consistingof LiPF₆, LiBF₄, LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄), LiP(C₂O₄)₃, LiBF₂(C₂O₄),LiB(C₂O₄)₂, LiPO₂F₂, LiN(POF₂)₂, LiN(FSO₂)(POF₂),LiN(FSO₂)(POF(OCH₂C≡CH)), LiN(FSO₂)₂, LiN(CF₃SO₂)₂, LiN(CF₃SO₂)(FSO₂),LiSO₃F, NaPF₆, NaBF₄, NaPF₂(C₂O₄)₂, NaPF₄(C₂O₄), NaP(C₂O₄)₃,NaBF₂(C₂O₄), NaB(C₂O₄)₂, NaPO₂F₂, NaN(POF₂)₂, NaN(FSO₂)(POF₂),NaN(FSO₂)(POF(OCH₂C≡CH)), NaN(FSO₂)₂, NaN(FSO₂)(FCO), NaN(CF₃SO₂)₂,NaN(CF₃SO₂)(FSO₂), and NaSO₃F.

The non-aqueous electrolyte solution may further contain at least oneselected from the group consisting of vinylene carbonate (hereinaftermay be referred to as “VC”), fluoroethylene carbonate,1,3,2-dioxathiolane 2,2-dioxide, tetravinylsilane, 1,3-propanesultone,ethynylethylene carbonate, trans-di fluoroethylene carbonate, and(ethoxy)pentafluorocyclotriphosphazene. When such a compound iscontained, at least any one of the cycle properties, high-temperaturestorage properties, and suppression of gas generation amount tends to beimproved. Among these compounds, in particular, it is preferable tocontain at least one selected from the group consisting of vinylenecarbonate, fluoroethylene carbonate, 1,3,2-dioxathiolane 2,2-dioxide,tetravinylsilane, and 1,3-propanesultone, from the viewpoint ofimproving at least any one of the cycle properties, high-temperaturestorage properties, and suppression of gas generation amount.

The lower limit of the content of the compound optionally contained inthe electrolyte solution is preferably 0.001 mass % or more, morepreferably 0.005 mass % or more, and further preferably 0.01 mass % ormore based on the total amount of the non-aqueous solvent, the solute,the additive for a non-aqueous electrolyte solution, and the “optionallycontained compound”, and the upper limit is preferably 5.0 mass % orless, more preferably 3.0 mass % or less, and further preferably 2.0mass % or less.

Incidentally, the “optionally contained compound” is described in theitem “other solute and additive” in the tables in Examples describedbelow.

In addition, the non-aqueous solvent is preferably at least one selectedfrom the group consisting of cyclic carbonates, chain carbonates, cyclicesters, chain esters, cyclic ethers, chain ethers, sulfone compounds,sulfoxide compounds, and ionic liquids.

In addition, the present invention relates to a non-aqueous electrolytesolution battery (hereinafter, may be referred to simply as a“non-aqueous battery” or “battery”) at least including a positiveelectrode, a negative electrode, and the above-described electrolytesolution.

Effect of the Invention

According to the present invention, it is possible to provide anadditive for a non-aqueous electrolyte solution that can exhibithigh-temperature cycle properties at 50° C. or more and low-temperatureoutput properties at −20° C. or less in a well-balanced manner, anon-aqueous electrolyte solution containing such an additive, as well asa non-aqueous electrolyte solution battery using such an electrolytesolution.

BRIEF DESCRIPTION BY THE DRAWINGS

FIG. 1 shows the results of evaluation of Examples 1-1 to 1-16 andComparative Examples 0 and 1-1 to 1-3;

FIG. 2 shows the results of evaluation of Examples 2-1 to 2-3 andComparative Examples 0 and 2-1 to 2-3;

FIG. 3 shows the results of evaluation of Examples 3-1 to 3-3 andComparative Examples 0 and 3-1 to 3-5; and

FIG. 4 shows the results of evaluation of Example 4-1 and ComparativeExamples 0 and 4-1 to 4-3.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described in detail below. However,the descriptions of the components described below are examples of theembodiments of the present invention, and the scope of the presentinvention is not limited to these specific contents and can be carriedout with various modifications within the scope of the gist of thepresent invention.

1. Additive for a Non-Aqueous Electrolyte Solution

Although the mechanism of the action of improving the battery propertiesby the present invention is not clear, it is conceived that the ioniccompound of the present invention is partially decomposed at theinterface between the positive electrode and the electrolyte solutionand the interface between the negative electrode and the electrolytesolution to form a film. It is conceived that this film inhibits thedirect contact between the non-aqueous solvent or the solute and theactive material to prevent the decomposition of the non-aqueous solventand the solute, so as to inhibit the deterioration of the batteryperformance.

Further, although the mechanism is not clear, it is important that theionic compound has both a N═P bond moiety and a sulfonyl moiety(S(═O)₂), and it is conceived that a firm film is formed byincorporating the N═P bond moiety and the sulfonyl moiety (S(═O)₂) intothe film. In addition, it is conceived that the charge in the film isbiased and that the film has a high lithium conductivity, that is, has alow resistance (the film has good output properties).

In addition, it is important that the ionic compound has at least oneP—F bond or S—F bond from the viewpoint of improving the low-temperatureproperties. It is conceived that when the above moiety includes a moietyhaving high electron-withdrawing properties (for example, a fluorineatom or a fluorine-containing alkyl group or alkoxy group), the chargebias is further increased and a film having a lower resistance (a filmhaving better output properties) is formed. A larger number of the P—Fbond and the S—F bond in the ionic compound is preferred from theviewpoint of improving the low-temperature properties. In particular, itis most preferable that Z¹ to Z⁴ all represent fluorine atoms from theviewpoint of improving the low-temperature properties.

From the above reasons, it is inferred that the effect of improving thehigh-temperature cycle properties and the low-temperature outputproperties in a well-balanced manner is exhibited by the non-aqueouselectrolyte solution containing the ionic compound of the presentinvention.

In the above formula [1], the groups represented by Z¹ to Z⁴ are asfollows. Examples of the alkyl group and the alkoxyl group include alkylgroups and fluorine-containing alkyl groups having 1 to 10 carbon atoms,such as a methyl group, an ethyl group, a propyl group, an isopropylgroup, a butyl group, a sec-butyl group, a tert-butyl group, a pentylgroup, a trifluoromethyl group, a 2,2-difluoroethyl group, a2,2,2-trifluoroethyl group, a 2,2,3,3-tetrafluoropropyl group, and a1,1,1,3,3,3-hexafluoroisopropyl group; and alkoxy groups derivedtherefrom.

Examples of the alkenyl group and the alkenyloxy group include alkenylgroups and fluorine-containing alkenyl groups having 2 to 10 carbonatoms, such as a vinyl group, an allyl group, a 1-propenyl group, anisopropenyl group, a 2-butenyl group, and a 1,3-butadienyl group; andalkenyloxy groups derived therefrom.

Examples of the alkynyl group and the alkynyloxy group include alkynylgroups and fluorine-containing alkynyl groups having 2 to 10 carbonatoms, such as an ethynyl group, a 2-propynyl group, and a1,1-dimethyl-2-propynyl group; and alkynyloxy groups derived therefrom.

Examples of the cycloalkyl group and the cycloalkoxy group includecycloalkyl groups and fluorine-containing cycloalkyl group having 3 to10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; andcycloalkoxy groups derived therefrom.

Examples of the cycloalkenyl group and the cycloalkenyloxy group includecycloalkenyl groups and fluorine-containing cycloalkenyl groups having 3to 10 carbon atoms, such as a cyclopentenyl group and a cyclohexenylgroup; and cycloalkenyloxy groups derived therefrom.

Examples of the aryl group and the aryloxy group include aryl groups andfluorine-containing aryl groups having 6 to 10 carbon atoms, such as aphenyl group, a tolyl group, and a xylyl group; and aryloxy groupsderived therefrom.

More specifically, examples of the anion of the ionic compoundrepresented by the above formula [1] include, but not limited to, thefollowing anions (1) to (16):

The ionic compound represented by formula [1] preferably has a highpurity. In particular, the content of chlorine (Cl) in the ioniccompound as a raw material before being dissolved in the electrolytesolution is preferably 5000 mass ppm or less, more preferably 1000 massppm or less, and further preferably 100 mass ppm or less. The use of theionic compound having a high concentration of remaining chlorine (Cl)tends to corrode the battery members and is therefore not preferred.Especially, a content of chloride (Cl) of higher than 5000 mass ppm maycorrode the current collector of the non-aqueous electrolyte solutionbattery and is not preferred.

In addition, the content of hydrofluoric acid in the ionic compoundrepresented by formula [1] as a raw material before being dissolved inthe electrolyte solution is preferably 5000 mass ppm or less and furtherpreferably 1000 mass ppm or less. The content of hydrofluoric acid ofhigher than 5000 mass ppm may corrode the current collector of thenon-aqueous electrolyte solution battery and is not preferred.

The ionic compound represented by formula [1] can be manufactured byvarious methods, and the manufacturing method is not particularlylimited.

For example, as described in Patent Document 2, the ionic compound canbe manufactured by reacting a corresponding phosphazo compound(Z¹SO₂N═PXZ²Z³ (X is a halogen atom)) and a corresponding sulfonylamidecompound (Z⁴SO₂NH-M) in the presence of an organic base or an inorganicbase in the absence of a solvent or in a solvent that does not reactwith them.

The ionic compound can also be obtained by synthesizingR¹SO₂N═P(R²)(R³)—NSO₂R⁴ and then converting R¹ to R⁴ into Z¹ to Z⁴,respectively, by a nucleophilic reaction.

2. Non-Aqueous Electrolyte Solution

2-1. Additive for Non-Aqueous Electrolyte Solution

The non-aqueous electrolyte solution of the present invention contains asolute and a non-aqueous solvent both of which will be described below,and the additive for a non-aqueous electrolyte solution described above.Based on the total amount of the non-aqueous solvent, the solute, andthe additive for a non-aqueous electrolyte solution, the lower limit ofthe content of the additive for a non-aqueous electrolyte solution inthe electrolyte solution is preferably 0.001 mass % or more, morepreferably 0.005 mass % or more, and further preferably 0.01 mass % ormore, and the upper limit is preferably 5.0 mass % or less, morepreferably 3.0 mass % or less, and further preferably 2.0 mass % orless.

If the content is lower than 0.001 mass %, since it is difficult tosufficiently obtain the effect of improving the battery properties, sucha content is not preferred. In contrast, if the content is higher than5.0 mass %, since a higher effect is not obtained, such a content isuseless, and also since the resistance is increased due to excessivefilm formation to lead to a risk of causing deterioration of the batteryperformance, such a content is not preferred. The above-described ioniccompounds as the additive for a non-aqueous electrolyte solution may beused alone or in any combination and at any ratio of two or morethereof, within a range not exceeding 5.0 mass % according to theapplication.

2-2. Solute

The type of the solute of the non-aqueous electrolyte solution of thepresent invention is not particularly limited, and any electrolyte saltcan be used. In a non-aqueous electrolyte solution for a metal cationbattery or a non-aqueous electrolyte solution for a capacitor, thesolute may be a salt having a metal cation or an onium cation as an ionsource. For example, in case of a lithium ion battery, the solute may bea lithium salt as the ion source. In case of a sodium ion battery, thesolute may be a sodium salt as the ion source. As the counter anionthereof, in view of the degree of dissociation in the non-aqueouselectrolyte solution, it is preferable to contain at least one selectedfrom the group consisting of PF₆ ⁻, BF₄ ⁻, PF₂(C₂O₄)₂ ⁻, PF₄(C₂O₄)⁻,P(C₂O₄)₃ ⁻, BF₂(C₂O₄)⁻, B(C₂O₄)₂ ⁻, PO₂F₂ ⁻, N(POF₂)₂ ⁻, N(FSO₂)(POF₂)⁻,N(FSO₂)(POF(OCH₂C≡CH))⁻, N(FSO₂)₂ ⁻, N(CF₃SO₂)₂ ⁻, N(CF₃SO₂)(FSO₂)⁻,SO₃F⁻, and N(FSO₂)(FCO)⁻. In particular, in view of the energy density,output properties, durability performance, etc. as a battery, use of acombination of two or more thereof is preferred.

Examples of the solute in a lithium battery and a lithium ion batteryinclude electrolyte salts, such as LiPF₆, LiBF₄, LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), LiP(C₂O₄)₃, LiBF₂(C₂O₄), LiB(C₂O₄)₂, LiPO₂F₂, LiN(POF₂)₂,LiN(FSO₂)(POF₂), LiN(FSO₂)(POF(OCH₂C≡CH)), LiN(FSO₂)₂, LiN(CF₃SO₂)₂,LiN(C₂F₅SO₂)₂, LiN(CF₃SO₂)(FSO₂), LiSO₃F, LiClO₄, LiAsF₆, LiSbF₆,LiCF₃SO₃, LiC(CF₃SO₂)₃, LiPF₃(C₃F₇)₃, LiB(CF₃)₄, and LiBF₃(C₂F₅).

In addition, examples of the solute in a sodium ion battery includeelectrolyte salts, such as NaPF₆, NaBF₄, NaPF₂(C₂O₄)₂, NaPF₄(C₂O₄),NaP(C₂O₄)₃, NaBF₂(C₂O₄), NaB(C₂O₄)₂, NaPO₂F₂, NaN(POF₂) 2,NaN(FSO₂)(POF₂), NaN(FSO₂)(POF(OCH₂C≡CH)), NaN(FSO₂)₂, NaN(CF₃SO₂)₂,NaN(C₂F₅SO₂)₂, NaN(CF₃SO₂)(FSO₂), NaSO₃F, NaN(FSO₂)(FCO), NaClO₄,NaAsF₆, NaSbF₆, NaCF₃SO₃, NaC(CF₃SO₂)₃, NaPF₃(C₃F₇)₃, NaB(CF₃)₄, andNaBF₃(C₂F₅).

These solutes may be used alone or in any combination and at any ratioof two or more thereof according to the application. In particular,considering the energy density, output properties, life duration, etc.as a battery, preferred are LiPF₆, LiBF₄, LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄),LiP(C₂O₄)₃, LiBF₂(C₂O₄), LiB(C₂O₄)₂, LiPO₂F₂, LiN(POF₂)₂,LiN(FSO₂)(POF₂), LiN(FSO₂)(POF(OCH₂C≡CH)), LiN(FSO₂)₂, LiN(CF₃SO₂)₂,LiN(CF₃SO₂)(FSO₂), LiSO₃F, NaPF₆, NaBF₄, NaPF₂(C₂O₄)₂, NaPF₄(C₂O₄),NaP(C₂O₄)₃, NaBF₂(C₂O₄), NaB(C₂O₄)₂, NaPO₂F₂, NaN(POF₂)₂,NaN(FSO₂)(POF₂), NaN(FSO₂)(POF(OCH₂C≡CH)), NaN(FSO₂)₂, NaN(CF₃SO₂)₂,NaN(CF₃SO₂)(FSO₂), and NaSO₃F.

A suitable combination of the solutes in a lithium battery and a lithiumion battery is preferably, for example, a combination of at least oneselected from the group consisting of LiBF₄, LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄),LiP(C₂O₄)₃, LiBF₂(C₂O₄), LiB(C₂O₄)₂, LiPO₂F₂, LiN(POF₂)₂,LiN(FSO₂)(POF₂), LiN(FSO₂)(POF(OCH₂C≡CH)), LiN(FSO₂)₂, LiN(CF₃SO₂)₂,LiN(CF₃SO₂)(FSO₂) and LiSO₃F, with LiPF₆. The ratio in the abovecombination (molar ratio when the LiPF₆ content is defined as 1 mole) isgenerally within a range of 1:0.001 to 1:0.5 and preferably 1:0.01 to1:0.2. The use of such a combination of the solutes at theabove-mentioned ratio provides an effect of further improving variousbattery properties. In contrast, when the ratio of LiPFE is lower than1:0.5, the ionic conductance of the electrolyte solution decreases, andthe resistance tends to increase.

The concentration of these solutes is not particularly limited, and thelower limit thereof is preferably 0.5 mol/L or more, more preferably 0.7mol/L or more, and further preferably 0.9 mol/L or more, and the upperlimit is preferably 2.5 mol/L or less, more preferably 2.0 mol/L orless, and further preferably 1.5 mol/L or less. When the concentrationis less than 0.5 mol/L, the ionic conductance decreases, and thereby thecycle properties and output properties of the non-aqueous electrolytesolution battery tend to be reduced. In contrast, when the concentrationis higher than 2.5 mol/L, the viscosity of the non-aqueous electrolytesolution increases, and thereby the ionic conductance likewise tends tobe reduced, and the cycle properties and output properties of thenon-aqueous-electrolyte solution battery may be reduced.

If a large amount of the above solute is dissolved at once in anon-aqueous solvent, the temperature of the non-aqueous electrolytesolution may be increased due to the heat of dissolution of the solute.When the solution temperature is significantly increased, thedecomposition of the lithium salt containing a fluorine atom isaccelerated, and hydrogen fluoride may be generated. Hydrogen fluoridebecomes a cause of deterioration of the battery performance and istherefore not preferred. Accordingly, the solution temperature when thesolute is dissolved in a non-aqueous solvent is not particularly limitedbut is preferably −20° C. to 80° C. and more preferably 0° C. to 60° C.

2-3. Non-Aqueous Solvent

The type of the non-aqueous solvent used in the non-aqueous electrolytesolution of the present invention is not particularly limited, and anynon-aqueous solvent can be used. Examples of the non-aqueous solventinclude cyclic carbonates, such as propylene carbonate, ethylenecarbonate, and butylene carbonate; chain carbonates, such as diethylcarbonate, dimethyl carbonate, and ethyl methyl carbonate; cyclicesters, such as γ-butyrolactone and γ-valerolactone; chain esters, suchas methyl acetate and methyl propionate; cyclic ethers, such astetrahydrofuran, 2-methyltetrahydrofuran, and dioxane; chain ethers,such as dimethoxyethane and diethyl ether; and sulfone compounds andsulfoxide compounds, such as dimethyl sulfoxide and sulfolane. Inaddition, for example, ionic liquids whose category differs from that ofthe non-aqueous solvent can be used. In addition, the non-aqueoussolvents used in the present invention may be used alone or may be usedin any combination and at any ratio of two or more thereof according tothe application. Among these non-aqueous solvents, from the viewpoint ofthe electrochemical stability against their redox and the chemicalstability related to the heat and the reaction with the solute,propylene carbonate, ethylene carbonate, diethyl carbonate, dimethylcarbonate, and ethyl methyl carbonate are especially preferred.

For example, it is preferable to use a combination of one or moreselected from cyclic carbonates having a high dielectric constant andone or more selected from chain carbonates or chain esters having a lowliquid viscosity as the non-aqueous solvent, because such a combinationincreases the ionic conductance of the electrolyte solution.

2-4. Other Additives

The above is the description about the basic composition of thenon-aqueous electrolyte solution of the present invention. Any additivesthat have been generally used may be added to the non-aqueouselectrolyte solution of the present invention at any ratio within arange that does not impair the gist of the present invention. Examplesof such additives include compounds that have overcharge preventioneffect, negative electrode film-forming effect, and positive electrodeprotection effect, such as methylene methanedisulfonate,1,2-ethanedisulfonic acid anhydride, 1,6-diisocyanatohexane,succinonitrile, cyclohexylbenzene, biphenyl, t-butylbenzene,vinylethylene carbonate, difluoroanisole, and dimethylvinylenecarbonate.

Further, a metal salt other than the above-mentioned solutes (lithiumsalts and sodium salts) may be used as an additive. Examples of themetal salt include carboxylic acid salts, such as lithium acrylate,sodium acrylate, lithium methacrylate, and sodium methacrylate; andsulfuric acid ester salts, such as lithium methyl sulfate, sodium methylsulfate, lithium ethyl sulfate, and sodium ethyl sulfate.

In addition, the non-aqueous electrolyte solution can also be used in astate which is quasi-solidified with a gelling agent or a cross-linkingpolymer as in case of being used in a non-aqueous electrolyte solutionbattery called a lithium polymer battery.

3. Non-Aqueous Electrolyte Solution Battery

The non-aqueous electrolyte solution battery of the present invention atleast includes (i) the above-described non-aqueous electrolyte solution,(ii) a positive electrode, and (iii) a negative electrode including atleast one selected from the group consisting of negative electrodematerials containing lithium metal and negative electrode materialscapable of occluding and releasing lithium, sodium, potassium, ormagnesium. The non-aqueous electrolyte solution battery preferablyfurther includes, for example, (iv) a separator and an outer case.

Positive Electrode (ii)

The positive electrode (ii) preferably includes at least one oxideand/or a polyanion compound as the positive electrode active material.

Positive Electrode Active Material

In a lithium ion secondary battery in which the main cation in thenon-aqueous electrolyte solution is lithium, the positive electrodeactive material constituting the positive electrode (ii) may be anymaterial that can be charged and discharged. Examples thereof includethose containing at least one selected from (A) a lithium-transitionmetal composite oxide containing at least one metal selected fromnickel, manganese, and cobalt and having a layered structure, (B) alithium-manganese composite oxide having a spinel structure, (C) alithium-containing olivine type phosphate, and (D) a lithium-richlayered transition metal oxide having a layered rock salt typestructure.

(A) Lithium-Transition Metal Composite Oxide

Examples of the positive electrode active material (A): thelithium-transition metal composite oxide containing at least one metalselected from nickel, manganese, and cobalt and having a layeredstructure, include a lithium-cobalt composite oxide, a lithium-nickelcomposite oxide, a lithium-nickel-cobalt composite oxide, alithium-nickel-cobalt-aluminum composite oxide, alithium-cobalt-manganese composite oxide, a lithium-nickel-manganesecomposite oxide, and a lithium-nickel-manganese-cobalt composite oxide.In addition, those obtained by substituting a part of the transitionmetal atoms that are the main components of these lithium-transitionmetal composite oxides with other elements, such as Al, Ti, V, Cr, Fe,Cu, Zn, Mg, Ga, Zr, Si, B, Ba, Y, and Sn, may be used.

As the lithium-cobalt composite oxide or the lithium-nickel compositeoxide, specifically, for example, LiCoO₂, LiNiO₂, lithium cobaltatedoped with different elements such as Mg, Zr, Al, or Ti (e.g.,LiCo_(0.98)Mg_(0.01)Zr_(0.01)O₂, LiCo_(0.98)Mg_(0.01)Al_(0.01)O₂, orLiCo_(0.975)Mg_(0.01)Zr_(0.005)Al_(0.1)O₂), or lithium cobaltate with arare earth compound fixed on the surface described in WO 2014/034043 maybe used. As described in JP-A-2002-151077, LiCoO₂ particle powder havingparticle surfaces partially coated with aluminum oxide may be used.

The lithium-nickel-cobalt composite oxide and thelithium-nickel-cobalt-aluminum composite oxide are represented byformula [1-1]:Li_(a)Ni_(1-b-c)CO_(b)M¹ _(c)O₂  [1-1]

In formula [1-1], M¹ is at least one element selected from the groupconsisting of Al, Fe, Mg, Zr, Ti, and B; a is 0.9≤a≤1.2; and b and csatisfy 0.1≤b≤0.3 and 0≤c≤0.1.

These composite oxides can be prepared in accordance with, for example,the manufacturing method described in JP-A-2009-137834. Specifically,examples of the composite oxides include LiNi_(0.8)Co_(0.2)O₂,LiNi_(0.85)Co_(0.01)Al_(0.05)O₂, LiNi_(0.87)Co_(0.10)Al_(0.03)O₂, andLiNi_(0.6)Co_(0.3)Al_(0.1)O₂.

Examples of the lithium-cobalt-manganese composite oxide and thelithium-nickel-manganese composite oxide include LiNi_(0.5)Mn_(0.5)O₂and LiCo_(0.5)Mn_(0.5)O₂.

Examples of the lithium-nickel-manganese-cobalt composite oxide includelithium-containing composite oxides represented by formula [1-2]:Li_(d)Ni_(e)Mn_(f)Co_(g)M² _(h)O₂  [1-2]

In formula [1-2], M² is at least one element selected from the groupconsisting of Al, Fe, Mg, Zr, Ti, B, and Sn; d is 0.9≤d≤1.2; and e, f,g, and h satisfy e+f+g+h=1, 0≤e≤0.8, 0≤f≤0.5, 0≤g≤0.5, and h≥0.

The lithium-nickel-manganese-cobalt composite oxide preferably containsmanganese within the range shown in formula [1-2] for increasing thestructural stability and improving the safety of the lithium secondarybattery at high temperature and more preferably further contains cobaltwithin the range shown in formula [1-2] for particularly increasing thehigh efficiency properties of the lithium ion secondary battery.

Specifically, examples of the lithium-nickel-manganese-cobalt compositeoxide include Li[Ni_(1/3)Mn_(1/3)Co_(1/3)]O₂,Li[Ni_(0.45)Mn_(0.35)Co_(0.2)]O₂, Li[Ni_(0.5)Mn_(0.3)Co_(0.2)]O₂,Li[Ni_(0.6)Mn_(0.2)Co_(0.2)]O₂,Li[Ni_(0.49)Mn_(0.3)Co_(0.2)Zr_(0.01)]O₂, andLi[Ni_(0.49)Mn_(0.3)Co_(0.2)Mg_(0.01)]O₂, which have a charge-dischargeregion of 4.3 V or more.

(B) Lithium-Manganese Composite Oxide Having Spinel Structure

Examples of the positive electrode active material (B): thelithium-manganese composite oxide having a spinel structure, includespinel lithium-manganese composite oxides represented by formula [1-3]:Li_(j)(Mn_(2-k)M³ _(k))O₄  [1-3]

In formula [1-3], M³ is at least one metal element selected from thegroup consisting of Ni, Co, Fe, Mg, Cr, Cu, Al, and Ti; j is1.05≤j≤1.15; and k is 0≤k≤0.20. Specifically, examples of thereofinclude LiMn₂O₄, LiMn_(1.95)Al_(0.05)O₄, LiMn_(1.9)Al_(0.1)O₄,LiMn_(1.9)Ni_(0.1)O₄, and LiMn_(1.5)Ni_(0.5)O₄.

(C) Lithium-Containing Olivine Type Phosphate Examples of the positiveelectrode active material (C): the lithium-containing olivine typephosphate, include those represented by formula [1-4]:LiFe_(1-n)M⁴ _(n)PO₄  [1-4]

In formula [1-4], M⁴ is at least one selected from Co, Ni, Mn, Cu, Zn,Nb, Mg, Al, Ti, W, Zr, and Cd; and n is 0≤n≤1.

Specifically, examples thereof include LiFePO₄, LiCoPO₄, LiNiPO₄, andLiMnPO₄, and in particular, LiFePO₄ and/or LiMnPO₄ is preferred.

(D) Lithium-Rich Layered Transition Metal Oxide

Examples of the positive electrode active material (D): the lithium-richlayered transition metal oxide having a layered rock salt typestructure, include those represented by formula [1-5]:xLiM⁵O₂·(1−x)Li₂M⁶O₃  [1-5]

In formula [1-5], x is a number satisfying 0<x<1; M⁵ is at least onemetal element having an average oxidation number of +3; and M⁶ is atleast one metal element having an average oxidation number of +4. Informula [1-5], M⁵ is preferably one trivalent metal element selectedfrom Mn, Ni, Co, Fe, V, and Cr and may be composed of equal amounts ofdivalent and tetravalent metals and having an average oxidation numberof +3.

In addition, in formula [1-5], M⁶ is preferably at least one metalelement selected from Mn, Zr, and Ti. Specifically, they include0.5[LiNi_(0.5)Mn_(0.5)O₂]·0.5[Li₂MnO₃],0.5[LiNi_(1/3)Co_(1/3)Mn_(1/3)O₂]·0.5[Li₂MnO₃],0.5[LiNi_(0.375)Co_(0.25)Mn_(0.375)O₂]·0.5[Li₂MnO₃],0.5[LiNi_(0.375)CO_(0.125)Fe_(0.125)Mn_(0.375)O₂]·0.5[Li₂MnO₃], and 0.45[LiNi_(0.375)Co_(0.25)Mn_(0.375)O₂]·0.10[Li₂TiO₃]·0.45 [Li₂MnO₃].

The positive electrode active material (D) represented by formula [1-5]is known to show a high capacity when charged at a high voltage of 4.4 V(based on Li) or more (for example, U.S. Pat. No. 7,135,252).

These positive electrode active materials can be prepared in accordancewith the manufacturing method described in, for example,JP-A-2008-270201, WO 2013/118661, or JP-A-2013-030284.

The positive electrode active material may include at least one selectedfrom the above compounds (A) to (D) as the main component, and examplesof other components include transition element chalcogenide, such asFeS₂, TiS₂, TiO₂, V₂O₅, MoO₃, and MoS₂; conductive polymers, such aspolyacetylene, polyparaphenylene, polyaniline, and polypyrrole;activated carbon; polymers generating radicals; and carbon materials.

Positive Electrode Current Collector

The positive electrode (ii) includes a positive electrode currentcollector. As the positive electrode current collector, for example,aluminum, stainless steel, nickel, titanium, or an alloy thereof can beused.

Positive Electrode Active Material Layer

In the positive electrode (ii), for example, a positive electrode activematerial layer is formed on at least one surface of the positiveelectrode current collector. The positive electrode active materiallayer is composed of, for example, the above-mentioned positiveelectrode active material, a binder, and, as needed, a conductive agent.

Examples of the binder include polytetrafluoroethylene, polyvinylidenefluoride, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,styrene-butadiene rubber (SBR), carboxymethyl cellulose, methylcellulose, acetate phthalate cellulose, hydroxypropyl methyl cellulose,and polyvinyl alcohol.

As the conductive agent, for example, carbon materials, such asacetylene black, Ketjen black, furnace black, carbon fiber, graphite(granular graphite and flaky graphite), and fluorinated graphite, can beused. In the positive electrode, acetylene black and Ketjen black havinglow crystallinity are preferred.

Negative Electrode (iii)

The negative electrode material is not particularly limited, and in alithium battery and a lithium ion battery, for example, lithium metal,an alloy or an intermetallic compound of lithium metal and anothermetal, a variety of carbon materials (artificial graphite, naturalgraphite, etc.), a metal oxide, a metal nitride, tin (simple substance),a tin compound, silicon (simple substance), a silicon compound,activated carbon, and a conductive polymer are used.

The carbon materials are, for example, easily graphitizable carbon,hardly graphitizable carbon (hard carbon) having an interplanar distancebetween the (200) planes of 0.37 nm or more, and graphite having aninterplanar distance between the (002) planes of 0.34 nm or less. Morespecifically, the carbon materials are, for example, pyrolytic carbons,cokes, glassy carbon fibers, organic polymer compound fired products,activated carbon, and carbon blacks. Among these materials, the cokesinclude pitch coke, needle coke, and petroleum coke. The organic polymercompound fired product is a product obtained by firing and carbonizing,for example, a phenolic resin or a furan resin at an appropriatetemperature. Since the carbon materials hardly change the crystalstructure by occlusion and release of lithium, a high energy density andalso excellent cycle properties are preferably obtained. Incidentally,the shape of the carbon material may be any of fibrous, spherical,granular, and flaky shapes. In addition, amorphous carbon and a graphitematerial having a surface coated with amorphous carbon are morepreferable because the reactivity between the material surface and theelectrolyte solution is lowered.

The negative electrode (iii) preferably includes at least one negativeelectrode active material.

Negative Electrode Active Material

In case of a lithium ion secondary battery in which the main cation inthe non-aqueous electrolyte solution is lithium, the negative electrodeactive material constituting the negative electrode (iii) is a materialthat can dope and dedope lithium ions, and examples thereof includethose containing at least one selected from (E) carbon materials havinga lattice plane ((002) plane) d value of 0.340 nm or less determined byX-ray diffraction; (F) carbon materials having a lattice plane ((002)plane) d value of higher than 0.340 nm determined by X-ray diffraction;(G) oxides of one or more metals selected from Si, Sn, and Al; (H) oneor more metals selected from Si, Sn, and Al, alloys containing thesemetals, or alloys of these metals or alloys with lithium; and (I)lithium titanium oxides. These negative electrode active materials canbe used alone or in combination of two or more thereof.

(E) Carbon Material Having a Lattice Plane ((002) Plane) d Value of0.340 nm or Less Determined by X-Ray Diffraction

Examples of the negative electrode active material (E): the carbonmaterial having a lattice plane ((002) plane) d value of 0.340 nm orless determined by X-ray diffraction, include pyrolytic carbons, cokes(such as pitch coke, needle coke, and petroleum coke), graphites,organic polymer compound fired products (such as products obtained byfiring and carbonizing, for example, a phenolic resin or a furan resinat an appropriate temperature), carbon fibers, and activated carbon; andthose obtained by graphitization thereof. The carbon material is onehaving an interplanar distance between the (002) planes (d002) of 0.340nm or less measured by an X-ray diffraction method, and especially thecarbon material is preferably graphite having a true density of 1.70g/cm³ or more or a highly crystalline carbon material having propertiessimilar to those of the graphite.

(F) Carbon Material Having a Lattice Plane ((002) Plane) d Value ofHigher than 0.340 Nm Determined by X-Ray Diffraction

Examples of the negative electrode active material (F): the carbonmaterial having a lattice plane ((002) plane) d value of higher than0.340 nm determined by X-ray diffraction, include amorphous carbon,which is a carbon material hardly changing the stacking order even whenheat-treated at a high temperature of 2000° C. or more. Examples thereofinclude hardly graphitizable carbon (hard carbon), meso-carbonmicrobeads (MCMB) fired at 1500° C. or less, and meso-phase pitch carbonfibers (MCF).

(G) Oxide of One or More Metals Selected from Si, Sn, and Al

Examples of the negative electrode active material (G): the oxide of oneor more metals selected from Si, Sn, and Al, include oxides that candope and dedope lithium ions, such as silicon oxide and tin oxide.

For example, SiO_(x) having a structure in which ultrafine particles ofSi are dispersed in SiO₂ is known. If this material is used as thenegative electrode active material, since Si reacting with Li is in anultrafine particle form, charge and discharge are smoothly performed. Onthe other hand, the surface area of the SiO_(x) particle itself havingthe above structure is small. Therefore, when it is used as acomposition (paste) for forming a negative electrode active materiallayer, the coating properties and the adhesive properties thereof to thecurrent collector are satisfactory.

Incidentally, since SiO_(x) significantly changes the volume by chargeand discharge, both an increase in the capacity and good charge anddischarge cycle properties can be achieved by using SiO together withthe above-described graphite as the negative electrode active material(E) at a specific ratio as the negative electrode active material.

(H) One or More Metals Selected from Si, Sn, and Al, Alloys Containingthese Metals, or Alloys of these Metals or Alloys with Lithium

Examples of the negative electrode active material (H): one or moremetals selected from Si, Sn, and Al, alloys containing these metals, oralloys of these metals or alloys with lithium, include metals, such assilicon, tin, and aluminum, silicon alloys, tin alloys, and aluminumalloys, and materials obtained from these metals and alloys by alloyingwith lithium by charge and discharge can also be used.

Preferred examples include those described in, for example, WO2004/100293 or JP-A-2008-016424, e.g., metal simple substances, such assilicon (Si) and tin (Sn), (for example, in powder form); the metalalloys; compounds containing the metals; and alloys containing themetals and tin (Sn) and cobalt (Co). The use of such a metal in theelectrode can realize a high charge capacity and causes relatively smallexpansion and contraction of the volume associated with charge anddischarge and is therefore preferred. In addition, it is known that whenthese metals are used in the negative electrode of a lithium ionsecondary battery, the metals are alloyed with Li during charging toshow a high charge capacity, and the use of such a metal is alsopreferred on this point.

Furthermore, for example, a negative electrode active material formed ofsubmicron-diameter pillars of silicon or a negative electrode activematerial formed of fibers of silicon described in, for example, WO2004/042851 or WO 2007/083155 may be used.

(I) Lithium Titanium Oxide

Examples of the negative electrode active material (I): the lithiumtitanium oxide, include lithium titanate having a spinel structure andlithium titanate having a ramsdellite structure.

Examples of the lithium titanate having a spinel structure includeLi_(4+α)Ti₅O₁₂ (α changes within a range of 0≤α≤3 according to thecharge and discharge reaction). Examples of the lithium titanate havinga ramsdellite structure include Li_(2+β)Ti₃O₇ (β changes within a rangeof 0≤β≤3 according to the charge and discharge reaction). These negativeelectrode active materials can be prepared in accordance with themanufacturing method described in, for example, JP-A-2007-018883 or2009-176752.

For example, in case of a sodium ion secondary battery in which the maincation in the non-aqueous electrolyte solution is sodium, as thenegative electrode active material, hard carbon or an oxide, such asTiO₂, V₂O₅, or MoO₃, is used. For example, in case of a sodium ionsecondary battery in which the main cation in the non-aqueouselectrolyte solution is sodium, as the positive electrode activematerial, a sodium-containing transition metal composite oxide, such asNaFeO₂, NaCrO₂, NaNiO₂, NaMnO₂, or NaCoO₂; those in which the transitionmetals, such as Fe, Cr, Ni, Mn, and Co, of the sodium-containingtransition metal composite oxides are mixtures thereof; those in whichthe transition metals of the sodium-containing transition metalcomposite oxides are partially substituted by metals other thantransition metals; a phosphate compound of a transition metal, such asNa₂FeP₂O₇ or NaCo₃(PO₄)₂P₂O₇; a sulfide such as TiS₂ or FeS₂; aconductive polymer such as polyacetylene, polyparaphenylene,polyaniline, or polypyrrole; activated carbon; a polymer generatingradicals; or a carbon material is used.

Negative Electrode Current Collector

The negative electrode (iii) includes a negative electrode currentcollector. As the negative electrode current collector, for example,copper, stainless steel, nickel, or titanium, or an alloy thereof can beused.

Negative Electrode Active Material Layer

In the negative electrode (iii), for example, a negative electrodeactive material layer is formed on at least one surface of the negativeelectrode current collector. The negative electrode active materiallayer is composed of, for example, the above-mentioned negativeelectrode active material, a binder, and, as needed, a conductive agent.

Examples of the binder include polytetrafluoroethylene, polyvinylidenefluoride, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,styrene-butadiene rubber (SBR), carboxymethyl cellulose, methylcellulose, acetate phthalate cellulose, hydroxypropyl methyl cellulose,and polyvinyl alcohol.

As the conductive agent, for example, carbon materials, such asacetylene black, Ketjen black, furnace black, carbon fiber, graphite(granular graphite and flaky graphite), and fluorinated graphite, can beused.

Method for Manufacturing Electrodes (Positive Electrode (ii) andNegative Electrode (iii))

An electrode can be obtained by, for example, dispersing and kneading anactive material, a binder, and, as needed, a conductive agent atpredetermined amounts in a solvent such as N-methyl-2-pyrrolidone (NMP)or water, applying the resultant paste to a current collector, anddrying it to form an active material layer. The resultant electrode ispreferably compressed by a method such as roll pressing to adjust thedensity of the electrode to an appropriate level.

Separator (iv)

The above non-aqueous-electrolyte solution battery can include aseparator (iv). As a separator for preventing contact between thepositive electrode (ii) and the negative electrode (iii), a polyolefin,such as polypropylene or polyethylene, cellulose, paper, a non-wovenfabric made of, for example, glass fibers, or a porous sheet is used.These films are preferably microporous so that the electrolyte solutioncan permeate, and ions can easily pass therethrough.

An example of the polyolefin separator is a microporous polymer film,such as a porous polyolefin film, that electrically insulates thepositive electrode and the negative electrode from each other and allowslithium ions to pass therethrough. Specifically, as the porouspolyolefin film, for example, a porous polyethylene film may be usedalone, or a multilayer film in which a porous polyethylene film and aporous polypropylene film are stacked may be used. In addition, acomposite film of porous polyethylene film and polypropylene film isanother example.

Outer Case

In constructing a non-aqueous electrolyte solution battery, as the outercase of the non-aqueous electrolyte solution battery, for example, ametal can in, for example, a coin, cylinder, or square shape or alaminated outer case can be used. Examples of the material of the metalcan include nickel-plated steel, stainless steel, nickel-platedstainless steel, aluminum or an alloy thereof, nickel, and titanium.

As the laminated outer case, for example, an aluminum laminate film, anSUS laminate film, or a laminate film of a silica-coated, for example,polypropylene or polyethylene can be used.

The structure of the non-aqueous electrolyte solution battery accordingto the present embodiment is not particularly limited. For example, thestructure can be such that an electrode element in which a positiveelectrode and a negative electrode are disposed opposite each other anda non-aqueous electrolyte solution are contained in an outer case. Theshape of the non-aqueous electrolyte solution battery is notparticularly limited. An electrochemical device having a shape such as acoin, cylinder, or square shape, or an aluminum laminate sheet type isassembled from the above-mentioned elements.

EXAMPLES

The present invention will now be specifically described by way ofexamples, but the scope of the present invention is not limited by theexamples.

Lithium Ion Battery

Example 1-1

Preparation of Electrolyte Solution

Non-aqueous electrolyte solution No. Li(1)-1 was prepared by using amixed solvent of ethylene carbonate, dimethyl carbonate, and ethylmethyl carbonate at a volume ratio of 2.5:3:4.5 as a non-aqueous solventand dissolving LiPF₆ as a solute and a Li salt of Anion (1) as the aboveionic compound in the solvent such that the concentration of LiPF₆ was1.0 mol/L and that the concentration of the Li salt (the content of Cland the content of hydrofluoric acid in the ionic compound as a rawmaterial before being dissolved in the electrolyte solution were 70 massppm and 120 mass ppm, respectively) was 1.0 mass % based on the totalamount of the non-aqueous solvent, the solute, and the ionic compound.The above preparation was performed while maintaining the solutiontemperature within a range of 20° C. to 30° C. The conditions forpreparing the non-aqueous electrolyte solution are shown in Table 1.

Production of Battery

A battery was produced by using the above electrolyte solution,LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ as the positive electrode material, andgraphite as the negative electrode material, and the high-temperaturecycle properties and the low-temperature output properties of thebattery were actually evaluated. The battery for the test was producedas follows.

A LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ powder (90 mass %) was mixed withpolyvinylidene fluoride (hereinafter referred to as “PVDF”, 5 mass %) asa binder and acetylene black (5 mass %) as a conductive material, andN-methylpyrrolidone (hereinafter referred to as “NMP”) was further addedto the mixture to make a paste. This paste was applied onto aluminumfoil and was dried to form a positive electrode body for a test.

On the other hand, a graphite powder (90 mass %) was mixed with PVDF (10mass %) as a binder, and NMP was further added to the resultant mixtureto form a slurry. The slurry was applied onto copper foil and was driedat 120° C. for 12 hours to form a negative electrode body for a test.

A polyethylene separator was impregnated with the electrolyte solution,so as to assemble a 50 mAh battery with an aluminum laminated outercase.

High-Temperature Cycle Property Test (High-Temperature Durability)

A charge and discharge test at an environmental temperature of 55° C.was performed, and the cycle properties were evaluated. The battery wascharged to 4.3 V and discharged until 3.0 V, and a charge and dischargecycle was repeated at a current density of 5.7 mA/cm². The degree ofdegradation of the battery after 300 cycles was evaluated based on thedischarge capacity retention rate. The discharge capacity retention ratewas determined by the following expression.

Discharge Capacity Retention Rate after 300 Cycles:Discharge capacity retention rate (%)=[(discharge capacity after 300cycles)/(initial discharge capacity)]×100.Low-Temperature Output Property Test (Low-Temperature Properties)

Charge and discharge were performed at a current density of 0.38 mA/cm²up to a charge voltage upper limit of 4.3 V in an environmentaltemperature of 25° C. by a constant current/constant voltage method. Thedischarge capacity at this time was defined as discharge capacity A.Subsequently, the battery was charged at a current density of 0.38mA/cm² in an environmental temperature of −20° C. up to the chargevoltage upper limit of 4.3 V by a constant current/constant voltagemethod and was then discharged at a constant current density of 9.5mA/cm² until a discharge termination voltage of 3.0 V. The dischargecapacity at this time was defined as discharge capacity B. The valuedetermined from “[(discharge capacity B)/(discharge capacity A)]×100”was defined as high-output capacity retention rate (%), and thelow-temperature output properties of the battery were evaluated.

The results of evaluation of batteries are shown in Table 2 and FIG. 1 .Incidentally, the values of the discharge capacity retention rates aftercycles and the high-output capacity retention rates of the batteriesshown in Table 2 are relative values when the discharge capacityretention rate after cycles and the high-output capacity retention rateof a laminated battery produced using Electrolyte solution No. (0)described below were each defined as 100.

TABLE 1 Other solute Ionic compound and additive Conc. Solute Conc.Electrolyte Type of Counter [mass Conc. [mass solution No. anion cation%] Type [mol/L] Type %] Li (1)-1 (1) Li+ 1 LiPF₆ 1 — — Li (2)-1 (2) Li+1 LiPF₆ 1 — — Li (3)-1 (3) Li+ 1 LiPF₆ 1 — — Li (4)-1 (4) Li+ 1 LiPF₆ 1— — Li (5)-1 (5) Li+ 1 LiPF₆ 1 — — Li (6)-1 (6) Li+ 1 LiPF₆ 1 — — Li(7)-1 (7) Li+ 1 LiPF₆ 1 — — Li (8)-1 (8) Li+ 1 LiPF₆ 1 — — Li (9)-1 (9)Li+ 1 LiPF₆ 1 — — Li (10)-1 (10)  Li+ 1 LiPF₆ 1 — — Li (11)-1 (11)  Li+1 LiPF₆ 1 — — Li (12)-1 (12)  Li+ 1 LiPF₆ 1 — — Li (13)-1 (13)  Li+ 1LiPF₆ 1 — — Li (14)-1 (14)  Li+ 1 LiPF₆ 1 — — Li (15)-1 (15)  Li+ 1LiPF₆ 1 — — Li (16)-1 (16)  Li+ 1 LiPF₆ 1 — — (0) — — — LiPF₆ 1 — —(0)-VC-1 — — — LiPF₆ 1 VC 1 Li (17)-1 (17)  Li+ 1 LiPF₆ 1 — — Li (18)-1(18)  Li+ 1 LiPF₆ 1 — —

TABLE 2 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 1-1 Li(1)-1 LiNi_(0.6)Co_(0.2) Graphite 111 111 Example 1-2 Li (2)-1Mn_(0.2)O₂ 115 110 Example 1-3 Li (3)-1 119 108 Example 1-4 Li (4)-1 119125 Example 1-5 Li (5)-1 111 114 Example 1-6 Li (6)-1 118 110 Example1-7 Li (7)-1 116 110 Example 1-8 Li (8)-1 113 113 Example 1-9 Li (9)-1120 113 Example 1-10 Li (10)-1 119 114 Example 1-11 Li (11)-1 114 105Example 1-12 Li (12)-1 114 106 Example 1-13 Li (13)-1 115 115 Example1-14 Li (14)-1 116 112 Example 1-15 Li (15)-1 114 113 Example 1-16 Li(16)-1 114 112 Comparative (0) 100 100 Example 0 Comparative (0)-VC-1107 93 Example 1-1 Comparative Li (17)-1 113 102 Example 1-2 ComparativeLi (18)-1 102 100 Example 1-3 *Relative value when the result ofevaluation of Electrolyte solution No. (0) was defined as 100.

Examples 1-2 to 1-16 and Comparative Examples 0 and 1-1 to 1-3

Electrolyte solutions were each prepared by the same procedure as thatin Electrolyte solution No. Li(1)-1 except that the type of the anion ofthe ionic compound was changed as shown in Table 1. Incidentally, forthe ionic compounds used in the subsequent examples, the contents of Clwere all 200 mass ppm or less, and the contents of hydrofluoric acidwere all 450 mass ppm or less.

Electrolyte solution No. (0) was prepared by the same procedure as thatin electrolyte solution No. Li(1)-1 except that the ionic compound ofthe present invention was not added thereto.

Electrolyte solution No. (0)-VC-1 was prepared by the same procedure asthat in Electrolyte solution No. Li(1)-1 except that the ionic compoundof the present invention was not added thereto and vinylene carbonate(hereinafter, referred to as “VC”) was added instead.

Electrolyte solution No. Li(17)-1 and Electrolyte solution No. Li(18)-1were prepared by the same procedure as that in Electrolyte solution No.Li(1)-1 except that the ionic compound of the present invention was notadded thereto and Li salts represented by the following formulae (17)and (18), which are ionic compounds having the structures that do notcome under formula [1], were added instead.

The resultant electrolyte solutions were evaluated as in Example 1-1.The results of the evaluation are shown in Table 2 and FIG. 1 .

The comparison of the results above demonstrates:

for Examples 1-1 to 1-16 using electrolyte solutions containing theionic compound of the present invention, the high-temperature cycleproperties and the low-temperature output properties were both improvedas compared with Comparative Example 1-1 using an electrolyte solutionnot containing the ionic compound but instead containing VC as disclosedin Patent Document 1;

for Examples 1-1 to 1-16, the high-temperature cycle properties wereequal to or greater than those in Comparative Example 1-2 using anelectrolyte solution not containing the ionic compound but insteadcontaining the ionic compound (Li salt of formula (17)) as disclosed inExample 4 of Patent Document 2, and the low-temperature outputproperties were improved; and

for Examples 1-1 to 1-16, the high-temperature cycle properties and thelow-temperature output properties were both improved as compared withComparative Example 1-3 using an electrolyte solution not containing theionic compound but instead containing an ionic compound (Li salt offormula (18)) as disclosed in Example 15 of Patent Document 2.

Accordingly, it was confirmed that the high-temperature cycle propertiesand the low-temperature output properties can be exhibited in awell-balanced manner by using an electrolyte solution containing theionic compound of the present invention.

Further, for Examples 1-1 to 1-16, it was confirmed that thelow-temperature properties are improved with an increase in the totalnumber of P—F bonds and S—F bonds of the ionic compound added to theelectrolyte solution. That is, the effect of improving thelow-temperature properties was the highest in Example 1-4 usingelectrolyte solution No. Li(4)-1 containing the ionic compound having atotal of four bonds.

The effect was high in the following order: in Examples 1-5, 1-8 to1-10, and 1-13 to 1-16 using Electrolyte solution Nos. Li(5)-1, Li(8)-1,Li(9)-1, Li(10)-1, Li(13)-1, Li(14)-1, Li(15)-1, and Li(16)-1,respectively, containing ionic compounds each having a total of threebonds; in Examples 1-1 to 1-3, 1-6, and 1-7 using Electrolyte solutionNos. Li(1)-1, Li(2)-1, Li(3)-1, Li(6)-1, and Li(7)-1, respectively,containing ionic compounds each having a total of two bonds; and inExamples 1-11 and 1-12 using Electrolyte solution Nos. Li(11)-1 andLi(12)-1, respectively, containing ionic compounds each having a totalof one bond.

Examples and Comparative Examples Using Electrolyte Solutions HavingVariously Modified Compositions (1)

Electrolyte solutions were each prepared by the same procedure as thatin Electrolyte solution No. Li(1)-1 except that the type and theconcentration of the ionic compounds and the types and theconcentrations of other solutes and additives were variously changed asshown in Tables 3 to 8 and FIGS. 2 to 4 . The resultant electrolytesolutions were evaluated as in Example 1-1.

It was confirmed that also for the respective Examples, similarly, thehigh-temperature cycle properties and the low-temperature outputproperties can be exhibited in a well-balanced manner by using theelectrolyte solution containing the ionic compounds of the presentinvention.

TABLE 3 Other solute Ionic compound and additive Conc. Solute Conc.Electrolyte Type of Counter [mass Conc. [mass solution No. anion cation%] Type [mol/L] Type %] H (1)-0.1  (1) H+ 0.1 LiPF₆ 1 — — H (8)-0.1  (8)H+ 0.1 LiPF₆ 1 — — H (10)-0.1 (10) H+ 0.1 LiPF₆ 1 — — (0) — — — LiPF₆ 1— — (0)-VC-0.1 — — — LiPF₆ 1 VC 0.1 H (17)-0.1 (17) H+ 0.1 LiPF₆ 1 — — H(18)-0.1 (18) H+ 0.1 LiPF₆ 1 — —

TABLE 4 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 2-1 H(1)-0.1 LiNi_(0.6)Co_(0.2) Graphite 107 107 Example 2-2 H (8)-0.1Mn_(0.2)O₂ 110 107 Example 2-3 H (10)-0.1 111 107 Comparative (0) 100100 Example 0 Comparative (0)-VC-0.1 103 97 Example 2-1 Comparative H(17)-0.1 105 100 Example 2-2 Comparative H (18)-0.1 100 100 Example 2-3*Relative value when the result of evaluation of Electrolyte solutionNo. (0) was defined as 100.

TABLE 5 Other solute Ionic compound and additive Conc. Solute Conc.Electrolyte Type of Counter [mass Conc. [mass solution No. anion cation%] Type [mol/L] Type %] H (2)-0.2  (2) H+ 0.2 LiPF₆ 1 — — H (4)-0.2  (4)H+ 0.2 LiPF₆ 1 — — Et4P (7)-0.2  (7) Et₄P+ 0.2 LiPF₆ 1 — — (0) — — —LiPF₆ 1 — — (0)-VC-0.2 — — — LiPF₆ 1 VC 0.2 H (17)-0.2 (17) H+ 0.2 LiPF₆1 — — H (18)-0.2 (18) H+ 0.2 LiPF₆ 1 — — Et4P (17)-0.2 (17) Et₄P+ 0.2LiPF₆ 1 — — Et4P (18)-0.2 (18) Et₄P+ 0.2 LiPF₆ 1 — —

TABLE 6 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 3-1 H(2)-0.2 LiNi_(0.6)Co_(0.2) Graphite 107 108 Example 3-2 H (4)-0.2Mn_(0.2)O₂ 109 111 Example 3-3 Et4P (7)-0.2 114 107 Comparative (0) 100100 Example 0 Comparative (0)-VC-0.2 104 96 Example 3-1 Comparative H(17)-0.2 106 100 Example 3-2 Comparative H (18)-0.2 100 100 Example 3-3Comparative Et4P (17)-0.2 107 100 Example 3-4 Comparative Et4P (18)-0.2100 100 Example 3-5 *Relative value when the result of evaluation ofElectrolyte solution No. (0) was defined as 100.

TABLE 7 Other solute Ionic compound and additive Conc. Solute Conc.Electrolyte Type of Counter [mass Conc. [mass solution No. anion cation%] Type [mol/L] Type %] Et4N (5)-0.5  (5) Et₄N+ 0.5 LiPF₆ 1 — — (0) — —— LiPF₆ 1 — — (0)-VC-0.5 — — — LiPF₆ 1 VC 0.5 Et4N (17)-0.5 (17) Et₄N+0.5 LiPF₆ 1 — — Et4N (18)-0.5 (18) Et₄N+ 0.5 LiPF₆ 1 — —

TABLE 8 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 4-1Et4N (5)-0.5 LiNi_(0.6)Co_(0.2) Graphite 107 111 Comparative (0)Mn_(0.2)O₂ 100 100 Example 0 Comparative (0)-VC-0.5 106 94 Example 4-1Comparative Et4N (17)-0.5 108 101 Example 4-2 Comparative Et4N (18)-0.5101 100 Example 4-3 *Relative value when the result of evaluation ofElectrolyte solution No. (0) was defined as 100.Examples and Comparative Examples Using Electrolyte Solutions HavingVariously Modified Compositions (2)

Electrolyte solutions were each prepared by the same procedure as thatin Electrolyte solution No. Li(1)-1 except that the types and theconcentrations of the ionic compounds, the types and the concentrationsof other solutes and additives, and the concentration of LiPF₆ werevariously changed as shown in Tables 9 to 22. The resultant electrolytesolutions were evaluated as in Example 1-1.

It was confirmed that also for each of Examples, similarly, thehigh-temperature cycle properties and the low-temperature outputproperties can be exhibited in a well-balanced manner by using theelectrolyte solution containing the ionic compound of the presentinvention.

TABLE 9 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.05-LiPF2(Ox)2-1  (2) Li+ 0.05 LiPF₆ 1LiPF₂(C₂O₄)₂ 1 Li (4)-0.05-LiPF2(Ox)2-1  (4) Li+ 0.05 LiPF₆ 1LiPF₂(C₂O₄)₂ 1 Li (6)-0.05-LiPF2(Ox)2-1  (6) Li+ 0.05 LiPF₆ 1LiPF₂(C₂O₄)₂ 1 Li (9)-0.05-LiPF2(Ox)2-1  (9) Li+ 0.05 LiPF₆ 1LiPF₂(C₂O₄)₂ 1 Li (15)-0.05-LiPF2(Ox)2-1 (15) Li+ 0.05 LiPF₆ 1LiPF₂(C₂O₄)₂ 1 (0)-LiPF2(Ox)2-1 — — — LiPF₆ 1 LiPF₂(C₂O₄)₂ 1(0)-LiPF2(Ox)2-1-VC-0.05 — — — LiPF₆ 1 LiPF₂(C₂O₄)₂, 1, 0.05 VC Li(17)-0.05-LiPF2(Ox)2-1 (17) Li+ 0.05 LiPF₆ 1 LiPF₂(C₂O₄)₂ 1 Li(18)-0.05-LiPF2(Ox)2-1 (18) Li+ 0.05 LiPF₆ 1 LiPF₂(C₂O₄)₂ 1 Li(2)-0.05-LiPF4(Ox)-1  (2) Li+ 0.05 LiPF₆ 1 LiPF₄(C₂O₄) 1 Li(2)-0.01-LiPF4(Ox)-1  (2) Li+ 0.01 LiPF₆ 1 LiPF₄(C₂O₄) 1 Li(2)-0.001-LiPF4(Ox)-1  (2) Li+  0.001 LiPF₆ 1 LiPF₄(C₂O₄) 1(0)-LiPF4(Ox)-1 — — — LiPF₆ 1 LiPF₄(C₂O₄) 1 (0)-LiPF4(Ox)-1-VC-0.05 — —— LiPF₆ 1 LiPF₄(C₂O₄), 1, 0.05 VC Li (17)-0.05-LiPF4(Ox)-1 (17) Li+ 0.05LiPF₆ 1 LiPF₄(C₂O₄) 1 Li (18)-0.05-LiPF4(Ox)-1 (18) Li+ 0.05 LiPF₆ 1LiPF₄(C₂O₄) 1 (0)-LiPF4(Ox)-1-VC-0.01 — — — LiPF₆ 1 LiPF₄(C₂O₄), 1, 0.01VC Li (17)-0.01-LiPF4(Ox)-1 (17) Li+ 0.01 LiPF₆ 1 LiPF₄(C₂O₄) 1 Li(18)-0.01-LiPF4(Ox)-1 (18) Li+ 0.01 LiPF₆ 1 LiPF₄(C₂O₄) 1(0)-LiPF4(Ox)-1-VC-0.001 — — — LiPF₆ 1 LiPF₄(C₂O₄),  1, 0.001 VC Li(17)-0.001-LiPF4(Ox)-1 (17) Li+  0.001 LiPF₆ 1 LiPF₄(C₂O₄) 1 Li(18)-0.001-LiPF4(Ox)-1 (18) Li+  0.001 LiPF₆ 1 LiPF₄(C₂O₄) 1 Li(4)-0.05-LiBF2(Ox)-1  (4) Li+ 0.05 LiPF₆ 1 LiBF₂(C₂O₄) 1 Li(4)-0.01-LiBF2(Ox)-1  (4) Li+ 0.01 LiPF₆ 1 LiBF₂(C₂O₄) 1 Li(4)-0.001-LiBF2(Ox)-1  (4) Li+  0.001 LiPF₆ 1 LiBF₂(C₂O₄) 1(0)-LiBF2(Ox)-1 — — — LiPF₆ 1 LiBF₂(C₂O₄) 1 (0)-LiBF2(Ox)-1-VC-0.05 — —— LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.05 VC Li (17)-0.05-LiBF2(Ox)-1 (17) Li+ 0.05LiPF₆ 1 LiBF₂(C₂O₄) 1 Li (18)-0.05-LiBF2(Ox)-1 (18) Li+ 0.05 LiPF₆ 1LiBF₂(C₂O₄) 1 (0)-LiBF2(Ox)-1-VC-0.01 — — — LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.01VC Li (17)-0.01-LiBF2(Ox)-1 (17) Li+ 0.01 LiPF₆ 1 LiBF₂(C₂O₄) 1 Li(18)-0.01-LiBF2(Ox)-1 (18) Li+ 0.01 LiPF₆ 1 LiBF₂(C₂O₄) 1(0)-LiBF2(Ox)-1-VC-0.001 — — — LiPF₆ 1 LiBF₂(C₂O₄),  1, 0.001 VC Li(17)-0.001-LiBF2(Ox)-1 (17) Li+  0.001 LiPF₆ 1 LiBF₂(C₂O₄) 1 Li(18)-0.001-LiBF2(Ox)-1 (18) Li+  0.001 LiPF₆ 1 LiBF₂(C₂O₄) 1

TABLE 10 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.5-LiPO2F2-1-[1.1] (2) Li+ 0.5 LiPF₆ 1.1LiPO₂F₂ 1 Li (4)-0.5-LiPO2F2-1-[1.1] (4) Li+ 0.5 LiPF₆ 1.1 LiPO₂F₂ 1 Li(6)-0.5-LiPO2F2-1-[1.1] (6) Li+ 0.5 LiPF₆ 1.1 LiPO₂F₂ 1 Li(9)-0.5-LiPO2F2-1-[1.1] (9) Li+ 0.5 LiPF₆ 1.1 LiPO₂F₂ 1 Li(15)-0.5-LiPO2F2-1-[1.1] (15)  Li+ 0.5 LiPF₆ 1.1 LiPO₂F₂ 1(0)-LiPO2F2-1-[1.1] — — — LiPF₆ 1.1 LiPO₂F₂ 1 (0)-LiPO2F2-1-VC-0.5-[1.1]— — — LiPF₆ 1.1 LiPO₂F₂, VC 1, 0.5  Li (17)-0.5-LiPO2F2-1-[1.1] (17) Li+ 0.5 LiPF₆ 1.1 LiPO₂F₂ 1 Li (18)-0.5-LiPO2F2-1-[1.1] (18)  Li+ 0.5LiPF₆ 1.1 LiPO₂F₂ 1 Li (2)-0.2-LiSO3F-1 (2) Li+ 0.2 LiPF₆ 1 LiSO₃F 1 Li(4)-0.2-LiSO3F-1 (4) Li+ 0.2 LiPF₆ 1 LiSO₃F 1 Li (9)-0.2-LiSO3F-1 (9)Li+ 0.2 LiPF₆ 1 LiSO₃F 1 (0)-LiSO3F-1 — — — LiPF₆ 1 LiSO₃F 1(0)-LiSO3F-1-VC-0.2 — — — LiPF₆ 1 LiSO₃F, VC 1, 0.2  Li(17)-0.2-LiSO3F-1 (17)  Li+ 0.2 LiPF₆ 1 LiSO₃F 1 Li (18)-0.2-LiSO3F-1(18)  Li+ 0.2 LiPF₆ 1 LiSO₃F 1 Li (4)-0.02-LiN(SO2F)2-3- (4) Li+ 0.02LiPF₆ 0.8 LiN(SO₂F)₂ 3 [0.8] Li (6)-0.02-LiN(SO2F)2-3- (6) Li+ 0.02LiPF₆ 0.8 LiN(SO₂F)₂ 3 [0.8] (0)-LiN(SO2F)2-3-[0.8] — — — LiPF₆ 0.8LiN(SO₂F)₂ 3 (0)-LiN(SO2F)2-3-VC-0.02- — — — LiPF₆ 0.8 LiN(SO₂F)₂, VC 3,0.02 [0.8] Li (17)-0.02-LiN(SO2F)2-3- (17)  Li+ 0.02 LiPF₆ 0.8LiN(SO₂F)₂ 3 [0.8] Li (18)-0.02-LiN(SO2F)2-3- (18)  Li+ 0.02 LiPF₆ 0.8LiN(SO₂F)₂ 3 [0.8] Li (2)-0.02- (2) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1LiN(SO2F)(POF2)-1 Li (4)-0.02- (4) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1LiN(SO2F)(POF2)-1 Li (6)-0.02- (6) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1LiN(SO2F)(POF2)-1 Li (9)-0.02- (9) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1LiN(SO2F)(POF2)-1 Li (15)-0.02- (15)  Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1LiN(SO2F)(POF2)-1 (0)-LiN(SO2F)(POF2)-1 — — — LiPF₆ 1 LiN(SO₂F)(POF₂) 1(0)-LiN(SO2F)(POF2)-1-VC- — — — LiPF₆ 1 LiN(SO₂F)(POF₂), VC 1, 0.02 0.02Li (17)-0.02- (17)  Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1 LiN(SO2F)(POF2)-1Li (18)-0.02- (18)  Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1 LiN(SO2F)(POF2)-1Li (2)-0.01- (2) Li+ 0.01 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)) 1LiN(FSO2)(POFpropynyloxy)-1 Li (4)-0.01- (4) Li+ 0.01 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)) 1 LiN(FSO2)(POFpropynyloxy)-1 Li (15)-0.01-(15)  Li+ 0.01 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)) 1LiN(FSO2)(POFpropynyloxy)-1 (0)- — — — LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)) 1LiN(FSO2)(POFpropynyloxy)-1 (0)- — — — LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)),1, 0.01 LiN(FSO2)(POFpropynyloxy)-1-VC-0.01 VC Li (17)-0.01- (17)  Li+0.01 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)) 1 LiN(FSO2)(POFpropynyloxy)-1 Li(18)-0.01- (18)  Li+ 0.01 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)) 1LiN(FSO2)(POFpropynyloxy)-1

TABLE 11 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.5-VC-1 (2) Li+ 0.5 LiPF₆ 1 VC 1 Li(4)-0.5-VC-1 (4) Li+ 0.5 LiPF₆ 1 VC 1 Li (6)-0.5-VC-1 (6) Li+ 0.5 LiPF₆1 VC 1 Li (9)-0.5-VC-1 (9) Li+ 0.5 LiPF₆ 1 VC 1 Li (15)-0.5-VC-1 (15) Li+ 0.5 LiPF₆ 1 VC 1 (0)-VC-1 — — — LiPF₆ 1 VC 1 (0)-VC-1.5 — — — LiPF₆1 VC 1.5 Li (17)-0.5-VC-1 (17)  Li+ 0.5 LiPF₆ 1 VC 1 Li (18)-0.5-VC-1(18)  Li+ 0.5 LiPF₆ 1 VC 1 Li (2)-0.5-PS-0.5 (2) Li+ 0.5 LiPF₆ 1 PS 0.5Li (4)-0.5-PS-0.5 (4) Li+ 0.5 LiPF₆ 1 PS 0.5 Li (6)-0.5-PS-0.5 (6) Li+0.5 LiPF₆ 1 PS 0.5 Li (9)-0.5-PS-0.5 (9) Li+ 0.5 LiPF₆ 1 PS 0.5 Li(15)-0.5-PS-0.5 (15)  Li+ 0.5 LiPF₆ 1 PS 0.5 (0)-PS-0.5 — — — LiPF₆ 1 PS0.5 (0)-PS-0.5-VC-0.5 — — — LiPF₆ 1 PS, VC 0.5, 0.5 Li (17)-0.5-PS-0.5(17)  Li+ 0.5 LiPF₆ 1 PS 0.5 Li (18)-0.5-PS-0.5 (18)  Li+ 0.5 LiPF₆ 1 PS0.5 Li (2)-0.5-DTDO-1 (2) Li+ 0.5 LiPF₆ 1 DTDO 1 Li (4)-0.5-DTDO-1 (4)Li+ 0.5 LiPF₆ 1 DTDO 1 Li (6)-0.5-DTDO-1 (6) Li+ 0.5 LiPF₆ 1 DTDO 1 Li(9)-0.5-DTDO-1 (9) Li+ 0.5 LiPF₆ 1 DTDO 1 Li (15)-0.5-DTDO-1 (15)  Li+0.5 LiPF₆ 1 DTDO 1 (0)-DTDO-1 — — — LiPF₆ 1 DTDO 1 (0)-DTDO-1-VC-0.5 — —— LiPF₆ 1 DTDO, VC   1, 0.5 Li (17)-0.5-DTDO-1 (17)  Li+ 0.5 LiPF₆ 1DTDO 1 Li (18)-0.5-DTDO-1 (18)  Li+ 0.5 LiPF₆ 1 DTDO 1 Li(2)-0.5-V4Si-0.2 (2) Li+ 0.5 LiPF₆ 1 V4Si 0.2 Li (4)-0.5-V4Si-0.2 (4)Li+ 0.5 LiPF₆ 1 V4Si 0.2 Li (6)-0.5-V4Si-0.2 (6) Li+ 0.5 LiPF₆ 1 V4Si0.2 Li (9)-0.5-V4Si-0.2 (9) Li+ 0.5 LiPF₆ 1 V4Si 0.2 Li(15)-0.5-V4Si-0.2 (15)  Li+ 0.5 LiPF₆ 1 V4Si 0.2 (0)-V4Si-0.2 — — —LiPF₆ 1 V4Si 0.2 (0)-V4Si-0.2-VC-0.5 — — — LiPF₆ 1 V4Si, VC 0.2, 0.5 Li(17)-0.5-V4Si-0.2 (17)  Li+ 0.5 LiPF₆ 1 V4Si 0.2 Li (18)-0.5-V4Si-0.2(18)  Li+ 0.5 LiPF₆ 1 V4Si 0.2 Li (2)-0.5-FEC-1 (2) Li+ 0.5 LiPF₆ 1 FEC1 Li (4)-0.5-FEC-1 (4) Li+ 0.5 LiPF₆ 1 FEC 1 Li (6)-0.5-FEC-1 (6) Li+0.5 LiPF₆ 1 FEC 1 Li (9)-0.5-FEC-1 (9) Li+ 0.5 LiPF₆ 1 FEC 1 Li(15)-0.5-FEC-1 (15)  Li+ 0.5 LiPF₆ 1 FEC 1 (0)-FEC-1 — — — LiPF₆ 1 FEC 1(0)-FEC-1 -VC-0.5 — — — LiPF₆ 1 FEC, VC   1, 0.5 Li (17)-0.5-FEC-1 (17) Li+ 0.5 LiPF₆ 1 FEC 1 Li (18)-0.5-FEC-1 (18)  Li+ 0.5 LiPF₆ 1 FEC 1

TABLE 12 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.02-LiPF2(Ox)2-0.2- (2) Li+ 0.02 LiPF₆ 1LiPF₂(C₂O₄)₂, 0.2, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (4)-0.02-LiPF2(Ox)2-0.2-(4) Li+ 0.02 LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li(6)-0.02-LiPF2(Ox)2-0.2- (6) Li+ 0.02 LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (9)-0.02-LiPF2(Ox)2-0.2- (9) Li+ 0.02 LiPF₆ 1LiPF₂(C₂O₄)₂, 0.2, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (15)-0.02-LiPF2(Ox)2-(15)  Li+ 0.02 LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1 0.2-LiPF4(Ox)-1 LiPF₄(C₂O₄)(0)-LiPF2(Ox)2-0.2- — — — LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1 LiPF4(Ox)-1LiPF₄(C₂O₄) (0)-LiPF2(Ox)2-0.2- — — — LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1,LiPF4(Ox)-1-VC-0.02 LiPF₄(C₂O₄), 0.02 VC Li (17)-0.02-LiPF2(Ox)2- (17) Li+ 0.02 LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 1 0.2-LiPF4(Ox)-1 LiPF₄(C₂O₄) Li(18)-0.02-LiPF2(Ox)2- (18)  Li+ 0.02 LiPF₆ 1 LiPF₂(C₂O₄)₂, 0.2, 10.2-LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (2)-0.02-VC-0.5- (2) Li+ 0.02 LiPF₆ 1 VC,0.5, 1 LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂ Li (4)-0.02-VC-0.5- (4) Li+ 0.02 LiPF₆1 VC, 0.5, 1 LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂ Li (6)-0.02-VC-0.5- (6) Li+ 0.02LiPF₆ 1 VC, 0.5, 1 LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂ Li (9)-0.02-VC-0.5- (9) Li+0.02 LiPF₆ 1 VC, 0.5, 1 LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂ Li (15)-0.02-VC-0.5-(15)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂(0)-VC-0.5-LiPF2(Ox)2-1 — — — LiPF₆ 1 VC, 0.5, 1 LiPF₂(C₂O₄)₂(0)-VC-0.52-LiPF2(Ox)2-1 — — — LiPF₆ 1 VC, 0.52, 1  LiPF₂(C₂O₄)₂ Li(17)-0.02-VC-0.5- (17)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiPF2(Ox)2-1LiPF₂(C₂O₄)₂ Li (18)-0.02-VC-0.5- (18)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1LiPF2(Ox)2-1 LiPF₂(C₂O₄)₂ Li (2)-0.02-VC-0.5- (2) Li+ 0.02 LiPF₆ 1 VC,0.5, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (4)-0.02-VC-0.5- (4) Li+ 0.02 LiPF₆ 1VC, 0.5, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (6)-0.02-VC-0.5- (6) Li+ 0.02LiPF₆ 1 VC, 0.5, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (9)-0.02-VC-0.5- (9) Li+0.02 LiPF₆ 1 VC, 0.5, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (15)-0.02-VC-0.5-(15)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiPF4(Ox)-1 LiPF₄(C₂O₄)(0)-VC-0.5-LiPF4(Ox)-1 — — — LiPF₆ 1 VC, 0.5, 1 LiPF₄(C₂O₄)(0)-VC-0.52-LiPF4(Ox)-1 — — — LiPF₆ 1 VC, 0.52, 1  LiPF₄(C₂O₄) Li(17)-0.02-VC-0.5- (17)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiPF4(Ox)-1LiPF₄(C₂O₄) Li (18)-0.02-VC-0.5- (18)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1LiPF4(Ox)-1 LiPF₄(C₂O₄) Li (2)-0.02-VC-0.5- (2) Li+ 0.02 LiPF₆ 1 VC,0.5, 1 LiBF2(Ox)-1 LiBF₂(C₂O₄) Li (4)-0.02-VC-0.5- (4) Li+ 0.02 LiPF₆ 1VC, 0.5, 1 LiBF2(Ox)-1 LiBF₂(C₂O₄) Li (6)-0.02-VC-0.5- (6) Li+ 0.02LiPF₆ 1 VC, 0.5, 1 LiBF2(Ox)-1 LiBF₂(C₂O₄) Li (9)-0.02-VC-0.5- (9) Li+0.02 LiPF₆ 1 VC, 0.5, 1 LiBF2(Ox)-1 LiBF₂(C₂O₄) Li (15)-0.02-VC-0.5-(15)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiBF2(Ox)-1 LiBF₂(C₂O₄)(0)-VC-0.5-LiBF2(Ox)-1 — — — LiPF₆ 1 VC, 0.5, 1 LiBF₂(C₂O₄)(0)-VC-0.52-LiBF2(Ox)-1 — — — LiPF₆ 1 VC, 0.52, 1  LiBF₂(C₂O₄) Li(17)-0.02-VC-0.5- (17)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1 LiBF2(Ox)-1LiBF₂(C₂O₄) Li (18)-0.02-VC-0.5- (18)  Li+ 0.02 LiPF₆ 1 VC, 0.5, 1LiBF2(Ox)-1 LiBF₂(C₂O₄) Li (2)-0.05-VC-0.5- (2) Li+ 0.05 LiPF₆ 1 VC,LiPO₂F₂ 0.5, 1 LiPO2F2-1 Li (4)-0.05-VC-0.5- (4) Li+ 0.05 LiPF₆ 1 VC,LiPO₂F₂ 0.5, 1 LiPO2F2-1 Li (6)-0.05-VC-0.5- (6) Li+ 0.05 LiPF₆ 1 VC,LiPO₂F₂ 0.5, 1 LiPO2F2-1 Li (9)-0.05-VC-0.5- (9) Li+ 0.05 LiPF₆ 1 VC,LiPO₂F₂ 0.5, 1 LiPO2F2-1 Li (15)-0.05-VC-0.5- (15)  Li+ 0.05 LiPF₆ 1 VC,LiPO₂F₂ 0.5, 1 LiPO2F2-1 (0)-VC-0.5-LiPO2F2-1 — — — LiPF₆ 1 VC, LiPO₂F₂0.5, 1 (0)-VC-0.55-LiPO2F2-1 — — — LiPF₆ 1 VC, LiPO₂F₂ 0.55, 1  Li(17)-0.05-VC-0.5- (17)  Li+ 0.05 LiPF₆ 1 VC, LiPO₂F₂ 0.5, 1 LiPO2F2-1 Li(18)-0.05-VC-0.5- (18)  Li+ 0.05 LiPF₆ 1 VC, LiPO₂F₂ 0.5, 1 LiPO2F2-1

TABLE 13 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.2-LiBOB-1-LiPO2F2- (2) Li+ 0.2 LiPF₆ 1LiBOB, LiPO₂F₂ 1, 0.5 0.5 Li (4)-0.2-LiBOB-1-LiPO2F2- (4) Li+ 0.2 LiPF₆1 LiBOB, LiPO₂F₂ 1, 0.5 0.5 Li (6)-0.2-LiBOB-1-LiPO2F2- (6) Li+ 0.2LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 0.5 Li (9)-0.2-LiBOB-1-LiPO2F2- (9) Li+0.2 LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 0.5 Li (15)-0.2-LiBOB-1- (15)  Li+ 0.2LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 LiPO2F2-0.5 (0)-LiBOB-1-LiPO2F2-0.5 — — —LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 (0)-LiBOB-1-LiPO2F2-0.5- — — — LiPF₆ 1LiBOB, 1, 0.5, VC-0.2 LiPO₂F₂, VC 0.2 Li (17)-0.2-LiBOB-1- (17)  Li+ 0.2LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 LiPO2F2-0.5 Li (18)-0.2-LiBOB-1- (18)  Li+0.2 LiPF₆ 1 LiBOB, LiPO₂F₂ 1, 0.5 LiPO2F2-0.5 Li (2)-0.05-LiBF2(Ox)-1-(2) Li+ 0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2 LiPO2F2-0.2 LiPO₂F₂ Li(4)-0.05-LiBF2(Ox)-1- (4) Li+ 0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2LiPO2F2-0.2 LiPO₂F₂ Li (6)-0.05-LiBF2(Ox)-1- (6) Li+ 0.05 LiPF₆ 1LiBF₂(C₂O₄, 1, 0.2 LiPO2F2-0.2 LiPO₂F₂ Li (9)-0.05-LiBF2(Ox)-1- (9) Li+0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2 LiPO2F2-0.2 LiPO₂F₂ Li(15)-0.05-LiBF2(Ox)-1- (15)  Li+ 0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2LiPO2F2-0.2 LiPO₂F₂ (0)-LiBF2(Ox)-1-LiPO2F2- — — — LiPF₆ 1 LiBF₂(C₂O₄),1, 0.2 0.2 LiPO₂F₂ (0)-LiBF2(Ox)-1-LiPO2F2- — — — LiPF₆ 1 LiBF₂(C₂O₄),1, 0.2, 0.2-VC-0.05 LiPO₂F₂, VC 0.05 Li (17)-0.05-LiBF2(Ox)-1- (17)  Li+0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2 LiPO2F2-0.2 LiPO₂F₂ Li(18)-0.05-LiBF2(Ox)-1- (18)  Li+ 0.05 LiPF₆ 1 LiBF₂(C₂O₄), 1, 0.2LiPO2F2-0.2 LiPO₂F₂ Li (2)-0.5-LiN(SO2F)2-3- (2) Li+ 0.5 LiPF₆ 1LiN(SO₂F)₂, 3, 0.5 LiPO2F2-0.5 LiPO₂F₂ Li (4)-0.5-LiN(SO2F)2-3- (4) Li+0.5 LiPF₆ 1 LiN(SO₂F)₂, 3, 0.5 LiPO2F2-0.5 LiPO₂F₂ Li(6)-0.5-LiN(SO2F)2-3- (6) Li+ 0.5 LiPF₆ 1 LiN(SO₂F)₂, 3, 0.5 LiPO2F2-0.5LiPO₂F₂ Li (9)-0.5-LiN(SO2F)2-3- (9) Li+ 0.5 LiPF₆ 1 LiN(SO₂F)₂, 3, 0.5LiPO2F2-0.5 LiPO₂F₂ Li (15)-0.5-LiN(SO2F)2-3- (15)  Li+ 0.5 LiPF₆ 1LiN(SO₂F)₂, 3, 0.5 LiPO2F2-0.5 LiPO₂F₂ (0)-LiN(SO2F)2-3-LiPO2F2- — — —LiPF₆ 1 LiN(SO₂F)_(2,) 3, 0.5 0.5 LiPO₂F₂ (0)-LiN(SO2F)2-3-LiPO2F2- — —— LiPF₆ 1 LiN(SO₂F)₂, 3, 0.5, 0.5-VC-0.5 LiPO₂F₂, VC 0.5 Li(17)-0.5-LiN(SO2F)2-3- (17)  Li+ 0.5 LiPF₆ 1 LiN(SO₂F)₂, 3, 0.5LiPO2F2-0.5 LiPO₂F₂ Li (18)-0.5-LiN(SO2F)2-3- (18)  Li+ 0.5 LiPF₆ 1LiN(SO₂F)₂, 3, 0.5 LiPO2F2-0.5 LiPO₂F₂ Li (2)-0.02- (2) Li+ 0.02 LiPF₆ 1LiN(SO₂F)(POF₂), 1, 0.1 LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1 Li(4)-0.02- (4) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂), 1, 0.1LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1 Li (6)-0.02- (6) Li+ 0.02 LiPF₆ 1LiN(SO₂F)(POF₂), 1, 0.1 LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1 Li(9)-0.02- (9) Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂) 1, 0.1 LiN(SO2F)(POF2)-1-LiPO₂F₂ LiPO2F2-0.1 Li (15)-0.02- (15)  Li+ 0.02 LiPF₆ 1LiN(SO₂F)(POF₂), 1, 0.1 LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1(0)-LiN(SO2F)(POF2)-1- — — — LiPF₆ 1 LiN(SO₂F)(POF₂), 1, 0.1 LiPO2F2-0.1LiPO₂F₂ (0)-LiN(SO2F)(POF2)-1- — — — LiPF₆ 1 LiN(SO₂F)(POF₂), 1, 0.1,LiPO2F2-0.1-VC-0.02 LiPO₂F₂, VC 0.02 Li (17)-0.02- (17)  Li+ 0.02 LiPF₆1 LiN(SO₂F)(POF₂), 1, 0.1 LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1 Li(18)-0.02- (18)  Li+ 0.02 LiPF₆ 1 LiN(SO₂F)(POF₂), 1, 0.1LiN(SO2F)(POF2)-1- LiPO₂F₂ LiPO2F2-0.1

TABLE 14 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (2) Li+ 0.5LiPF₆ 1 LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li(4)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (4) Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li(6)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (6) Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li(9)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (9) Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li(15)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (15)  Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC (0)-LiPF2(Ox)2-1-LiPF4(Ox)-0.2-VC-0.5— — — LiPF₆ 1 LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄), 1, 0.2, 0.5 VC(0)-LiPF2(Ox)2-1-LiPF4(Ox)-0.2-VC-1 — — — LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 1 VC Li (17)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (17) Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li(18)-0.5-LiPF2(Ox)2-1-LiPF4(Ox)-0.2- (18)  Li+ 0.5 LiPF₆ 1 LiPF₂(C₂O₄)₂,LiPF₄(C₂O₄), 1, 0.2, 0.5 VC-0.5 VC Li (2)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5-(2) Li+ 0.05 LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1LiN(SO2F)2-2-V4Si-0.1 V4Si Li (4)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (4) Li+0.05 LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1LiN(SO2F)2-2-V4Si-0.1 V4Si Li (6)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (6) Li+0.05 LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1LiN(SO2F)2-2-V4Si-0.1 V4Si Li (9)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (9) Li+0.05 LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1LiN(SO2F)2-2-V4Si-0.1 V4Si Li (15)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (15) Li+ 0.05 LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1LiN(SO2F)2-2-V4Si-0.1 V4Si (0)-LiBF4-0.2-LiBF2(Ox)-0.5-LiN(SO2F)2- — — —LiPF₆ 1 LiBF₄, LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1 2-V4Si-0.1 V4Si(0)-LiBF4-0.2-LiBF2(Ox)-0.5-LiN(SO2F)2- — — — LiPF₆ 1 LiBF₄,LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1, 2-V4Si-0.1-VC-0.05 V4Si, VC0.05 Li (17)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (17)  Li+ 0.05 LiPF₆ 1 LiBF₄,LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1 LiN(SO2F)2-2-V4Si-0.1 V4Si Li(18)-0.05-LiBF4-0.2-LiBF2(Ox)-0.5- (18)  Li+ 0.05 LiPF₆ 1 LiBF₄,LiBF₂(C₂O₄), LiN(SO₂F)₂, 0.2, 0.5, 2, 0.1 LiN(SO2F)2-2-V4Si-0.1 V4Si Li(2)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2- (2) Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F,LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 Li (4)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2-(4) Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F, LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 Li(6)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2- (6) Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F,LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 Li (9)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2-(9) Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F, LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 Li(15)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2- (15)  Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F,LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 (0)-LiBOB-1-LiSO3F-1-LiPO2F2-0.5-BP-2— — — LiPF₆ 1 LiBOB, LiSO₃F, LiPO₂F₂, BP 1, 1, 0.5, 2(0)-LiBOB-1-LiSO3F-1-LiPO2F2-0.5-BP-2- — — — LiPF₆ 1 LiBOB, LiSO₃F,LiPO₂F₂, BP, 1, 1, 0.5, 2, VC-0.2 VC 0.2 Li(17)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2- (17)  Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F,LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2 Li (18)-0.2-LiBOB-1-LiSO3F-1-LiPO2F2-(18)  Li+ 0.2 LiPF₆ 1 LiBOB, LiSO₃F, LiPO₂F₂, BP 1, 1, 0.5, 2 0.5-BP-2Li (2)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (2) Li+ 0.02 LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5 1-LiPO2F2-0.1-CHB-1.5LiPO₂F₂, CHB Li (4)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (4) Li+ 0.02LiPF₆ 1 LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.51-LiPO2F2-0.1-CHB-1.5 LiPO₂F₂, CHB Li(6)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (6) Li+ 0.02 LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5 1-LiPO2F2-0.1-CHB-1.5LiPO₂F₂, CHB Li (9)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (9) Li+ 0.02LiPF₆ 1 LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.51-LiPO2F2-0.1-CHB-1.5 LiPO₂F₂, CHB Li(15)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (15)  Li+ 0.02 LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5 1-LiPO2F2-0.1-CHB-1.5LiPO₂F₂, CHB (0)-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)-1- — — — LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5 LiPO2F2-0.1-CHB-1.5LiPO₂F₂, CHB (0)-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)-1- — — — LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5,LiPO2F2-0.1-CHB-1.5-VC-0.02 LiPO₂F₂, CHB, VC 0.02 Li(17)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (17)  Li+ 0.02 LiPF₆ 1LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.5 1-LiPO2F2-0.1-CHB-1.5LiPO₂F₂, CHB Li (18)-0.02-LiPF4(Ox)-1.5-LiN(SO2F)(POF2)- (18)  Li+ 0.02LiPF₆ 1 LiPF₄(C₂O₄), LiN(SO₂F)(POF₂), 1.5, 1, 0.1, 1.51-LiPO2F2-0.1-CHB-1.5 LiPO₂F₂, CHB

TABLE 15 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Li (2)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (2) Li+0.02 LiPF₆ 1 LiBF₂(C₂O₄), LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(4)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (4) Li+ 0.02 LiPF₆ 1 LiBF₂(C₂O₄),LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(6)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (6) Li+ 0.02 LiPF₆ 1 LiBF₂(C₂O₄),LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(9)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (9) Li+ 0.02 LiPF₆ 1 LiBF₂(C₂O₄),LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(15)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (15)  Li+ 0.02 LiPF₆ 1LiBF₂(C₂O₄), LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si(0)-LiBF2(Ox)-1-LiN(SO2F)(POF2)-1-V4Si- — — — LiPF₆ 1 LiBF₂(C₂O₄),LiN(SO₂F)(POF₂), 1, 1, 0.1 0.1 V4Si(0)-LiBF2(Ox)-1-LiN(SO2F)(POF2)-1-V4Si- — — — LiPF₆ 1 LiBF₂(C₂O₄),LiN(SO₂F)(POF₂), 1, 1, 0.1, 0.02 0.1-VC-0.02 V4Si, VC Li(17)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (17)  Li+ 0.02 LiPF₆ 1LiBF₂(C₂O₄), LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(18)-0.02-LiBF2(Ox)-1-LiN(SO2F)(POF2)- (18)  Li+ 0.02 LiPF₆ 1LiBF₂(C₂O₄), LiN(SO₂F)(POF₂), 1, 1, 0.1 1-V4Si-0.1 V4Si Li(2)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (2) Li+ 0.02 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2, LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5LiSO₃F, LiPO₂F₂, TBB 1.5 Li (4)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (4)Li+ 0.02 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2,LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 LiSO₃F, LiPO₂F₂, TBB 1.5 Li(6)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (6) Li+ 0.02 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2, LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5LiSO₃F, LiPO₂F₂, TBB 1.5 Li (9)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (9)Li+ 0.02 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2,LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 LiSO₃F, LiPO₂F₂, TBB 1.5 Li(15)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (15)  Li+ 0.02 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2, LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5LiSO₃F, LiPO₂F₂, TBB 1.5 (0)-LiN(FSO2)(POFpropynyloxy)-1- — — — LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2, LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5LiSO₃F, LiPO₂F₂, TBB 1.5 (0)-LiN(FSO2)(POFpropynyloxy)-1- — — — LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2,LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5-VC-0.02 LiSO₃F, LiPO₂F₂, TBB, VC 1.5,0.02 Li (17)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (17)  Li+ 0.02 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2, LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5LiSO₃F, LiPO₂F₂, TBB 1.5 Li (18)-0.02-LiN(FSO2)(POFpropynyloxy)-1- (18) Li+ 0.02 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.2,LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 LiSO₃F, LiPO₂F₂, TBB 1.5 Li(2)-0.01-LiN(FSO2)(POFpropynyloxy)-1- (2) Li+ 0.01 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1 LiPO2F2-0.2-DTDO-0.5-FEC-1LiPO₂F₂, DTDO, FEC Li (4)-0.01-LiN(FSO2)(POFpropynyloxy)-1- (4) Li+ 0.01LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1LiPO2F2-0.2-DTDO-0.5-FEC-1 LiPO₂F₂, DTDO, FEC Li(6)-0.01-LiN(FSO2)(POFpropynyloxy)-1- (6) Li+ 0.01 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1 LiPO2F2-0.2-DTDO-0.5-FEC-1LiPO₂F₂, DTDO, FEC Li (9)-0.01-LiN(FSO2)(POFpropynyloxy)-1- (9) Li+ 0.01LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1LiPO2F2-0.2-DTDO-0.5-FEC-1 LiPO₂F₂, DTDO, FEC Li(15)-0.01-LiN(FSO2)(POFpropynyloxy)-1- (15)  Li+ 0.01 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1 LiPO2F2-0.2-DTDO-0.5-FEC-1LiPO₂F₂, DTDO, FEC (0)-LiN(FSO2)(POFpropynyloxy)-1-LiPO2F2- — — — LiPF₆1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1 0.2-DTDO-0.5-FEC-1 LiPO₂F₂,DTDO, FEC (0)-LiN(FSO2)(POFpropynyloxy)-1-LiPO2F2- — — — LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1, 0.2-DTDO-0.5-FEC-1-VC-0.01LiPO₂F₂, DTDO, FEC, VC 0.01 Li (17)-0.01-LiN(FSO2)(POFpropynyloxy)-(17)  Li+ 0.01 LiPF₆ 1 LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 11-LiPO2F2-0.2-DTDO-0.5-FEC-1 LiPO₂F₂, DTDO, FEC Li(18)-0.01-LiN(FSO2)(POFpropynyloxy)- (18)  Li+ 0.01 LiPF₆ 1LiN(FSO₂)(POF(OCH₂CCH)), 1, 0.2, 0.5, 1 1-LiPO2F2-0.2-DTDO-0.5-FEC-1LiPO₂F₂, DTDO, FEC

TABLE 16 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 5-1 Li(2)-0.05-LiPF2(Ox)2-1 LiNi_(0.6)Co_(0.2) Graphite 105 105 Example 5-2 Li(4)-0.05-LiPF2(Ox)2-1 Mn_(0.2)O₂ 106 109 Example 5-3 Li(6)-0.05-LiPF2(Ox)2-1 106 109 Example 5-4 Li (9)-0.05-LiPF2(Ox)2-1 107108 Example 5-5 Li (15)-0.05-LiPF2(Ox)2-1 108 107 Comparative(0)-LiPF2(Ox)2-1 100 100 Example 5-0 Comparative(0)-LiPF2(Ox)2-1-VC-0.05 101 99 Example 5-1 Comparative Li(17)-0.05-LiPF2(Ox)2-1 103 100 Example 5-2 Comparative Li(18)-0.05-LiPF2(Ox)2-1 100 100 Example 5-3 Example 6-1 Li(2)-0.05-LiPF4(Ox)-1 107 108 Example 6-2 Li (2)-0.01-LiPF4(Ox)-1 104 105Example 6-3 Li (2)-0.001-LiPF4(Ox)-1 101 102 Comparative (0)-LiPF4(Ox)-1100 100 Example 6-0 Comparative (0)-LiPF4(Ox)-1-VC-0.05 101 98 Example6-1 Comparative Li (17)-0.05-LiPF4(Ox)-1 102 100 Example 6-2 ComparativeLi (18)-0.05-LiPF4(Ox)-1 100 100 Example 6-3 Comparative(0)-LiPF4(Ox)-1-VC-0.01 100 100 Example 6-4 Comparative Li(17)-0.01-LiPF4(Ox)-1 101 100 Example 6-5 Comparative Li(18)-0.01-LiPF4(Ox)-1 100 100 Example 6-6 Comparative(0)-LiPF4(Ox)-1-VC-0.001 100 99 Example 6-7 Comparative Li(17)-0.001-LiPF4(Ox)-1 100 100 Example 6-8 Comparative Li(18)-0.001-LiPF4(Ox)-1 100 100 Example 6-9 Example 7-1 Li(4)-0.05-LiBF2(Ox)-1 108 107 Example 7-2 Li (4)-0.01-LiBF2(Ox)-1 103 104Example 7-3 Li (4)-0.001-LiBF2(Ox)-1 103 103 Comparative (0)-LiBF2(Ox)-1100 100 Example 7-0 Comparative (0)-LiBF2(Ox)-1-VC-0.05 101 98 Example7-1 Comparative Li (17)-0.05-LiBF2(Ox)-1 102 100 Example 7-2 ComparativeLi (18)-0.05-LiBF2(Ox)-1 100 100 Example 7-3 Comparative(0)-LiBF2(Ox)-1-VC-0.01 100 100 Example 7-4 Comparative Li(17)-0.01-LiBF2(Ox)-1 101 100 Example 7-5 Comparative Li(18)-0.01-LiBF2(Ox)-1 100 100 Example 7-6 Comparative(0)-LiBF2(Ox)-1-VC-0.001 100 100 Example 7-7 Comparative Li(17)-0.001-LiBF2(Ox)-1 100 100 Example 7-8 Comparative Li(18)-0.001-LiBF2(Ox)-1 100 100 Example 7-9 *In Examples 5-1 to 5-5 andComparative Examples 5-1 to 5-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 5-0 was defined as100. *In Examples 6-1 to 6-3 and Comparative Examples 6-1 to 6-9, thevalues were each a relative value when the result of evaluation inComparative Example 6-0 was defined as 100. *In Examples 7-1 to 7-3 andComparative Examples 7-1 to 7-9, the values were each a relative valuewhen the result of evaluation in Comparative Example 7-0 was defined as100.

TABLE 17 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 8-1 Li(2)-0.5-LiPO2F2-1-[1.1] LiNi_(0.6)Co_(0.2) Graphite 112 109 Example 8-2Li (4)-0.5-LiPO2F2-1-[1.1] Mn_(0.2)O₂ 112 117 Example 8-3 Li(6)-0.5-LiPO2F2-1-[1.1] 113 109 Example 8-4 Li (9)-0.5-LiPO2F2-1-[1.1]111 111 Example 8-5 Li (15)-0.5-LiPO2F2-1-[1.1] 114 111 Comparative(0)-LiPO2F2-1-[1.1] 100 100 Example 8-0 Comparative(0)-LiPO2F2-1-VC-0.5-[1.1] 107 91 Example 8-1 Comparative Li(17)-0.5-LiPO2F2-1-[1.1] 107 101 Example 8-2 Comparative Li(18)-0.5-LiPO2F2-1-[1.1] 100 100 Example 8-3 Example 9-1 Li(2)-0.2-LiSO3F-1 111 109 Example 9-2 Li (4)-0.2-LiSO3F-1 110 115 Example9-3 Li (9)-0.2-LiSO3F-1 109 111 Comparative (0)-LiSO3F-1 100 100 Example9-0 Comparative (0)-LiSO3F-1-VC-0.2 104 93 Example 9-1 Comparative Li(17)-0.2-LiSO3F-1 105 101 Example 9-2 Comparative Li (18)-0.2-LiSO3F-1100 100 Example 9-3 Example 10-1 Li (4)-0.02-LiN(SO2F)2-3-[0.8] 105 106Example 10-2 Li (6)-0.02-LiN(SO2F)2-3-[0.8] 105 104 Comparative(0)-LiN(SO2F)2-3-[0.8] 100 100 Example 10-0 Comparative(0)-LiN(SO2F)2-3-VC-0.02-[0.8] 100 99 Example 10-1 Comparative Li(17)-0.02-LiN(SO2F)2-3-[0.8] 100 100 Example 10-2 Comparative Li(18)-0.02-LiN(SO2F)2-3-[0.8] 100 100 Example 10-3 Example 11-1 Li(2)-0.02-LiN(SO2F)(POF2)-1 104 106 Example 11-2 Li(4)-0.02-LiN(SO2F)(POF2)-1 105 106 Example 11-3 Li(6)-0.02-LiN(SO2F)(POF2)-1 103 105 Example 11-4 Li(9)-0.02-LiN(SO2F)(POF2)-1 104 104 Example 11-5 Li(15)-0.02-LiN(SO2F)(POF2)-1 105 103 Comparative (0)-LiN(SO2F)(POF2)-1100 100 Example 11-0 Comparative (0)-LiN(SO2F)(POF2)-1-VC-0.02 100 100Example 11-1 Comparative Li (17)-0.02-LiN(SO2F)(POF2)-1 101 100 Example11-2 Comparative Li (18)-0.02-LiN(SO2F)(POF2)-1 100 100 Example 11-3Example 12-1 Li (2)-0.01-LiN(FSO2)(POFpropynyloxy)-1 104 104 Example12-2 Li (4)-0.01-LiN(FSO2)(POFpropynyloxy)-1 103 104 Example 12-3 Li(15)-0.01-LiN(FSO2)(POFpropynyloxy)-1 102 103 Comparative(0)-LiN(FSO2)(POFpropynyloxy)-1 100 100 Example 12-0 Comparative(0)-LiN(FSO2)(POFpropynyloxy)-1-VC-0.01 100 100 Example 12-1 ComparativeLi (17)-0.01-LiN(FSO2)(POFpropynyloxy)-1 100 100 Example 12-2Comparative Li (18)-0.01-LiN(FSO2)(POFpropynyloxy)-1 100 100 Example12-3 *In Examples 8-1 to 8-5 and Comparative Examples 8-1 to 8-3, thevalues were each a relative value when the result of evaluation inComparative Example 8-0 was defined as 100. *In Examples 9-1 to 9-3 andComparative Examples 9-1 to 9-3, the values are each a relative valuewhen the result of evaluation in Comparative Example 9-0 was defined as100. *In Examples 10-1 and 10-2 and Comparative Examples 10-1 to 10-3,the values were each a relative value when the result of evaluation inComparative Example 10-0 was defined as 100. *In Examples 11-1 to 11-5and Comparative Examples 11-1 to 11-3, the values were each a relativevalue when the result of evaluation in Comparative Example 11-0 wasdefined as 100. *In Examples 12-1 to 12-3 and Comparative Examples 12-1to 12-3, the values were each a relative value when the result ofevaluation in Comparative Example 12-0 was defined as 100.

TABLE 18 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 13-1Li (2)-0.5-VC-1 LiNi_(0.6)Co_(0.2) Graphite 108 111 Example 13-2 Li(4)-0.5-VC-1 Mn_(0.2)O₂ 110 112 Example 13-3 Li (6)-0.5-VC-1 109 111Example 13-4 Li (9)-0.5-VC-1 109 108 Example 13-5 Li (15)-0.5-VC-1 110109 Comparative (0)-VC-1 100 100 Example 13-0 Comparative (0)-VC-1.5 10692 Example 13-1 Comparative Li (17)-0.5-VC-1 107 101 Example 13-2Comparative Li (18)-0.5-VC-1 100 100 Example 13-3 Example 14-1 Li(2)-0.5-PS-0.5 107 112 Example 14-2 Li (4)-0.5-PS-0.5 107 112 Example14-3 Li (6)-0.5-PS-0.5 107 108 Example 14-4 Li (9)-0.5-PS-0.5 108 107Example 14-5 Li (15)-0.5-PS-0.5 109 107 Comparative (0)-PS-0.5 100 100Example 14-0 Comparative (0)-PS-0.5-VC-0.5 107 93 Example 14-1Comparative Li (17)-0.5-PS-0.5 107 100 Example 14-2 Comparative Li(18)-0.5-PS-0.5 100 100 Example 14-3 Example 15-1 Li (2)-0.5-DTDO-1 108111 Example 15-2 Li (4)-0.5-DTDO-1 111 110 Example 15-3 Li(6)-0.5-DTDO-1 109 107 Example 15-4 Li (9)-0.5-DTDO-1 106 108 Example15-5 Li (15)-0.5-DTDO-1 109 107 Comparative (0)-DTDO-1 100 100 Example15-0 Comparative (0)-DTDO-1-VC-0.5 105 95 Example 15-1 Comparative Li(17)-0.5-DTDO-1 104 101 Example 15-2 Comparative Li (18)-0.5-DTDO-1 100100 Example 15-3 Example 16-1 Li (2)-0.5-V4Si-0.2 106 112 Example 16-2Li (4)-0.5-V4Si-0.2 109 115 Example 16-3 Li (6)-0.5-V4Si-0.2 107 109Example 16-4 Li (9)-0.5-V4Si-0.2 110 107 Example 16-5 Li(15)-0.5-V4Si-0.2 109 107 Comparative (0)-V4Si-0.2 100 100 Example 16-0Comparative (0)-V4Si-0.2-VC-0.5 104 90 Example 16-1 Comparative Li(17)-0.5-V4Si-0.2 105 100 Example 16-2 Comparative Li (18)-0.5-V4Si-0.2100 100 Example 16-3 Example 17-1 Li (2)-0.5-FEC-1 109 111 Example 17-2Li (4)-0.5-FEC-1 110 110 Example 17-3 Li (6)-0.5-FEC-1 108 109 Example17-4 Li (9)-0.5-FEC-1 110 107 Example 17-5 Li (15)-0.5-FEC-1 107 108Comparative (0)-FEC-1 100 100 Example 17-0 Comparative (0)-FEC-1-VC-0.5104 94 Example 17-1 Comparative Li (17)-0.5-FEC-1 105 101 Example 17-2Comparative Li (18)-0.5-FEC-1 100 100 Example 17-3 *In Examples 13-1 to13-5 and Comparative Examples 13-1 to 13-3, the values were each arelative value when the result of evaluation in Comparative Example 13-0was defined as 100. *In Examples 14-1 to 14-5 and Comparative Examples14-1 to 14-3, the values were each a relative value when the result ofevaluation in Comparative Example 14-0 was defined as 100. *In Examples15-1 to 15-5 and Comparative Examples 15-1 to 15-3, the values were eacha relative value when the result of evaluation in Comparative Example15-0 was defined as 100. *In Examples 16-1 to 16-5 and ComparativeExamples 16-1 to 16-3, the values were each a relative value when theresult of evaluation in Comparative Example 16-0 was defined as 100. *InExamples 17-1 to 17-5 and Comparative Examples 17-1 to 17-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 17-0 was defined as 100.

TABLE 19 Discharge capacity High-output Positive Negative retentioncapacity Electrolyte electrode electrode rate after retention solutionactive active cycles* rate* No. material material [%] [%] Example 18-1Li (2)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 LiNi_(0.6)Co_(0.2) Graphite 105104 Example 18-2 Li (4)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 Mn_(0.2)O₂ 106105 Example 18-3 Li (6)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 106 104 Example18-4 Li (9)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 104 103 Example 18-5 Li(15)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 104 103 Comparative(0)-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 100 100 Example 18-0 Comparative(0)-LiPF2(Ox)2-0.2-LiPF4(Ox)-1-VC-0.02 100 99 Example 18-1 ComparativeLi (17)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 101 100 Example 18-2 ComparativeLi (18)-0.02-LiPF2(Ox)2-0.2-LiPF4(Ox)-1 100 100 Example 18-3 Example19-1 Li (2)-0.02-VC-0.5-LiPF2(Ox)2-1 104 106 Example 19-2 Li(4)-0.02-VC-0.5-LiPF2(Ox)2-1 103 105 Example 19-3 Li(6)-0.02-VC-0.5-LiPF2(Ox)2-1 104 104 Example 19-4 Li(9)-0.02-VC-0.5-LiPF2(Ox)2-1 103 104 Example 19-5 Li(15)-0.02-VC-0.5-LiPF2(Ox)2-1 103 103 Comparative(0)-VC-0.5-LiPF2(Ox)2-1 100 100 Example 19-0 Comparative(0)-VC-0.52-LiPF2(Ox)2-1 100 100 Example 19-1 Comparative Li(17)-0.02-VC-0.5-LiPF2(Ox)2-1 100 100 Example 19-2 Comparative Li(18)-0.02-VC-0.5-LiPF2(Ox)2-1 100 100 Example 19-3 Example 20-1 Li(2)-0.02-VC-0.5-LiPF4(Ox)-1 103 104 Example 20-2 Li(4)-0.02-VC-0.5-LiPF4(Ox)-1 104 104 Example 20-3 Li(6)-0.02-VC-0.5-LiPF4(Ox)-1 104 103 Example 20-4 Li(9)-0.02-VC-0.5-LiPF4(Ox)-1 103 103 Example 20-5 Li(15)-0.02-VC-0.5-LiPF4(Ox)-1 104 102 Comparative (0)-VC-0.5-LiPF4(Ox)-1100 100 Example 20-0 Comparative (0)-VC-0.52-LiPF4(Ox)-1 100 100 Example20-1 Comparative Li (17)-0.02-VC-0.5-LiPF4(Ox)-1 101 100 Example 20-2Comparative Li (18)-0.02-VC-0.5-LiPF4(Ox)-1 100 100 Example 20-3 Example21-1 Li (2)-0.02-VC-0.5-LiBF2(Ox)-1 104 105 Example 21-2 Li(4)-0.02-VC-0.5-LiBF2(Ox)-1 104 105 Example 21-3 Li(6)-0.02-VC-0.5-LiBF2(Ox)-1 104 103 Example 21-4 Li(9)-0.02-VC-0.5-LiBF2(Ox)-1 103 103 Example 21-5 Li(15)-0.02-VC-0.5-LiBF2(Ox)-1 103 103 Comparative (0)-VC-0.5-LiBF2(Ox)-1100 100 Example 21-0 Comparative (0)-VC-0.52-LiBF2(Ox)-1 100 100 Example21-1 Comparative Li (17)-0.02-VC-0.5-LiBF2(Ox)-1 100 100 Example 21-2Comparative Li (18)-0.02-VC-0.5-LiBF2(Ox)-1 100 100 Example 21-3 Example22-1 Li (2)-0.05-VC-0.5-LiPO2F2-1 107 107 Example 22-2 Li(4)-0.05-VC-0.5-LiPO2F2-1 108 108 Example 22-3 Li(6)-0.05-VC-0.5-LiPO2F2-1 105 104 Example 22-4 Li(9)-0.05-VC-0.5-LiPO2F2-1 105 105 Example 22-5 Li(15)-0.05-VC-0.5-LiPO2F2-1 105 104 Comparative (0)-VC-0.5-LiP02F2-1 100100 Example 22-0 Comparative (0)-VC-0.55-LiP02F2-1 101 98 Example 22-1Comparative Li (17)-0.05-VC-0.5-LiPO2F2-1 101 100 Example 22-2Comparative Li (18)-0.05-VC-0.5-LiPO2F2-1 100 100 Example 22-3 *InExamples 18-1 to 18-5 and Comparative Examples 18-1 to 18-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 18-0 was defined as 100. *In Examples 19-1 to 19-5 andComparative Examples 19-1 to 19-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 19-0 was defined as100. *In Examples 20-1 to 20-5 and Comparative Examples 20-1 to 20-3,the values were each a relative value when the result of evaluation inComparative Example 20-0 was defined as 100. *In Examples 21-1 to 21-5and Comparative Examples 21-1 to 21-3, the values were each a relativevalue when the result of evaluation in Comparative Example 21-0 wasdefined as 100. *In Examples 22-1 to 22-5 and Comparative Examples 22-1to 22-3, the values were each a relative value when the result ofevaluation in Comparative Example 22-0 was defined as 100.

TABLE 20 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 23-1Li (2)-0.2-LiBOB-1- LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Graphite 110 111LiPO2F2-0.5 Example 23-2 Li (4)-0.2-LiBOB-1- 110 112 LiPO2F2-0.5 Example23-3 Li (6)-0.2-LiBOB-1- 108 107 LiPO2F2-0.5 Example 23-4 Li(9)-0.2-LiBOB-1- 107 109 LiPO2F2-0.5 Example 23-5 Li (15)-0.2-LiBOB-1-111 107 LiPO2F2-0.5 Comparative (0)-LiBOB-1-LiPO2F2-0.5 100 100 Example23-0 Comparative (0)-LiBOB-1-LiPO2F2-0.5- 103 96 Example 23-1 VC-0.2Comparative Li (17)-0.2-LiBOB-1- 104 100 Example 23-2 LiPO2F2-0.5Comparative Li (18)-0.2-LiBOB-1- 100 100 Example 23-3 LiPO2F2-0.5Example 24-1 Li (2)-0.05-LiBF2(Ox)-1- 107 106 LiPO2F2-0.2 Example 24-2Li (4)-0.05-LiBF2(Ox)-1- 106 107 LiPO2F2-0.2 Example 24-3 Li(6)-0.05-LiBF2(Ox)-1- 106 105 LiPO2F2-0.2 Example 24-4 Li(9)-0.05-LiBF2(Ox)-1- 108 105 LiPO2F2-0.2 Example 24-5 Li(15)-0.05-LiBF2(Ox)-1- 109 106 LiPO2F2-0.2 Comparative(0)-LiBF2(Ox)-1-LiPO2F2- 100 100 Example 24-0 0.2 Comparative(0)-LiBF2(Ox)-1-LiPO2F2- 101 100 Example 24-1 0.2-VC-0.05 Comparative Li(17)-0.05-LiBF2(Ox)-1- 100 100 Example 24-2 LiPO2F2-0.2 Comparative Li(18)-0.05-LiBF2(Ox)-1- 100 100 Example 24-3 LiPO2F2-0.2 Example 25-1 Li(2)-0.5-LiN(SO2F)2-3- 112 113 LiPO2F2-0.5 Example 25-2 Li(4)-0.5-LiN(SO2F)2-3- 113 114 LiPO2F2-0.5 Example 25-3 Li(6)-0.5-LiN(SO2F)2-3- 111 111 LiPO2F2-0.5 Example 25-4 Li(9)-0.5-LiN(SO2F)2-3- 112 109 LiPO2F2-0.5 Example 25-5 Li(15)-0.5-LiN(SO2F)2-3- 113 110 LiPO2F2-0.5 Comparative (0)-LiN(SO2F)2-3-100 100 Example 25-0 LiPO2F2-0.5 Comparative (0)-LiN(SO2F)2-3- 106 93Example 25-1 LiPO2F2-0.5-VC-0.5 Comparative Li (17)-0.5-LiN(SO2F)2-3-104 100 Example 25-2 LiPO2F2-0.5 Comparative Li (18)-0.5-LiN(SO2F)2-3-101 100 Example 25-3 LiPO2F2-0.5 Example 26-1 Li (2)-0.02- 106 107LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Example 26-2 Li (4)-0.02- 106 107LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Example 26-3 Li (6)-0.02- 104 103LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Example 26-4 Li (9)-0.02- 105 104LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Example 26-5 Li (15)-0.02- 105 103LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Comparative (0)-LiN(SO2F)(POF2)-1- 100100 Example 26-0 LiPO2F2-0.1 Comparative (0)-LiN(SO2F)(POF2)-1- 100 99Example 26-1 LiPO2F2-0.1-VC-0.02 Comparative Li (17)-0.02- 100 100Example 26-2 LiN(SO2F)(POF2)-1- LiPO2F2-0.1 Comparative Li (18)-0.02-100 100 Example 26-3 LiN(SO2F)(POF2)-1- LiPO2F2-0.1 *In Examples 23-1 to23-5 and Comparative Examples 23-1 to 23-3, the values were each arelative value when the result of evaluation in Comparative Example 23-0was defined as 100. *In Examples 24-1 to 24-5 and Comparative Examples24-1 to 24-3, the values were each a relative value when the result ofevaluation in Comparative Example 24-0 was defined as 100. *In Examples25-1 to 25-5 and Comparative Examples 25-1 to 25-3, the values were eacha relative value when the result of evaluation in Comparative Example25-0 was defined as 100. *In Examples 26-1 to 26-5 and ComparativeExamples 26-1 to 26-3, the values were each a relative value when theresult of evaluation in Comparative Example 26-0 was defined as 100.

TABLE 21 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 27-1Li (2)-0.5-LiPF2(Ox)2-1- LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Graphite 109 108LiPF4(Ox)-0.2-VC-0.5 Example 27-2 Li (4)-0.5-LiPF2(Ox)2-1- 111 113LiPF4(Ox)-0.2-VC-0.5 Example 27-3 Li (6)-0.5-LiPF2(Ox)2-1- 106 107LiPF4(Ox)-0.2-VC-0.5 Example 27-4 Li (9)-0.5-LiPF2(Ox)2-1- 107 110LiPF4(Ox)-0.2-VC-0.5 Example 27-5 Li (15)-0.5-LiPF2(Ox)2-1- 108 109LiPF4(Ox)-0.2-VC-0.5 Comparative (0)-LiPF2(Ox)2-1-LiPF4(Ox)- 100 100Example 27-0 0.2-VC-0.5 Comparative (0)-LiPF2(Ox)2-1-LiPF4(Ox)- 103 96Example 27-1 0.2-VC-1 Comparative Li (17)-0.5-LiPF2(Ox)2-1- 103 100Example 27-2 LiPF4(Ox)-0.2-VC-0.5 Comparative Li (18)-0.5-LiPF2(Ox)2-1-100 100 Example 27-3 LiPF4(Ox)-0.2-VC-0.5 Example 28-1 Li(2)-0.05-LiBF4-0.2-LiBF2(Ox)- 105 104 0.5-LiN(SO2F)2-2-V4Si-0.1 Example28-2 Li (4)-0.05-LiBF4-0.2-LiBF2(Ox)- 106 106 0.5-LiN(SO2F)2-2-V4Si-0.1Example 28-3 Li (6)-0.05-LiBF4-0.2-LiBF2(Ox)- 105 1030.5-LiN(SO2F)2-2-V4Si-0.1 Example 28-4 Li (9)-0.05-LiBF4-0.2-LiBF2(Ox)-105 104 0.5-LiN(SO2F)2-2-V4Si-0.1 Example 28-5 Li (15)-0.05-LiBF4-0.2-104 104 LiBF2(Ox)-0.5-LiN(SO2F)2-2- V4Si-0.1 Comparative(0)-LiBF4-0.2-LiBF2(Ox)-0.5- 100 100 Example 28-0 LiN(SO2F)2-2-V4Si-0.1Comparative (0)-LiBF4-0.2-LiBF2(Ox)-0.5- 100 100 Example 28-1LiN(SO2F)2-2-V4Si-0.1-VC-0.05 Comparative Li (17)-0.05-LiBF4-0.2- 100100 Example 28-2 LiBF2(Ox)-0.5-LiN(SO2F)2-2- V4Si-0.1 Comparative Li(18)-0.05-LiBF4-0.2- 100 100 Example 28-3 LiBF2(Ox)-0.5-LiN(SO2F)2-2-V4Si-0.1 Example 29-1 Li (2)-0.2-LiBOB-1-LiSO3F-1- 108 106LiPO2F2-0.5-BP-2 Example 29-2 Li (4)-0.2-LiBOB-1-LiSO3F-1- 110 110LiPO2F2-0.5-BP-2 Example 29-3 Li (6)-0.2-LiBOB-1-LiSO3F-1- 105 105LiPO2F2-0.5-BP-2 Example 29-4 Li (9)-0.2-LiBOB-1-LiSO3F-1- 105 107LiPO2F2-0.5-BP-2 Example 29-5 Li (15)-0.2-LiBOB-1-LiSO3F-1- 105 106LiPO2F2-0.5-BP-2 Comparative (0)-LiBOB-1-LiSO3F-1- 100 100 Example 29-0LiPO2F2-0.5-BP-2 Comparative (0)-LiBOB-1-LiSO3F-1- 101 96 Example 29-1LiPO2F2-0.5-BP-2-VC-0.2 Comparative Li (17)-0.2-LiBOB-1-LiSO3F-1- 102100 Example 29-2 LiPO2F2-0.5-BP-2 Comparative Li(18)-0.2-LiBOB-1-LiSO3F-1- 100 100 Example 29-3 LiPO2F2-0.5-BP-2 Example30-1 Li (2)-0.02-LiPF4(Ox)-1.5- 103 102 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5 Example 30-2 Li (4)-0.02-LiPF4(Ox)-1.5- 104 106LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 30-3 Li(6)-0.02-LiPF4(Ox)-1.5- 103 102 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Example 30-4 Li (9)-0.02-LiPF4(Ox)-1.5- 103 103LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 30-5 Li(15)-0.02-LiPF4(Ox)-1.5- 103 103 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Comparative (0)-LiPF4(Ox)-1.5- 100 100 Example 30-0LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative (0)-LiPF4(Ox)-1.5-100 100 Example 30-1 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5-VC-0.02Comparative Li (17)-0.02-LiPF4(Ox)-1.5- 100 100 Example 30-2LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative Li(18)-0.02-LiPF4(Ox)-1.5- 100 100 Example 30-3 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5 *In Examples 27-1 to 27-5 and Comparative Examples 27-1 to27-3, the values were each a relative value when the result ofevaluation in Comparative Example 27-0 was defined as 100. *In Examples28-1 to 28-5 and Comparative Examples 28-1 to 28-3, the values were eacha relative value when the result of evaluation in Comparative Example28-0 was defined as 100. *In Examples 29-1 to 29-5 and ComparativeExamples 29-1 to 29-3, the values were each a relative value when theresult of evaluation in Comparative Example 29-0 was defined as 100. *InExamples 30-1 to 30-5 and Comparative Examples 30-1 to 30-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 30-0 was defined as 100.

TABLE 22 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 31-1Li (2)-0.02-LiBF2(Ox)-1- LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Graphite 104 103LiN(SO2F)(POF2)-1-V4Si-0.1 Example 31-2 Li (4)-0.02-LiBF2(Ox)-1- 104 107LiN(SO2F)(POF2)-1-V4Si-0.1 Example 31-3 Li (6)-0.02-LiBF2(Ox)-1- 103 102LiN(SO2F)(POF2)-1-V4Si-0.1 Example 31-4 Li (9)-0.02-LiBF2(Ox)-1- 103 103LiN(SO2F)(POF2)-1-V4Si-0.1 Example 31-5 Li (15)-0.02-LiBF2(Ox)-1- 104104 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative(0)-LiBF2(Ox)-1-LiN(SO2F)(POF2)- 100 100 Example 31-0 1-V4Si-0.1Comparative (0)-LiBF2(Ox)-1-LiN(SO2F)(POF2)- 100 100 Example 31-11-V4Si-0.1-VC-0.02 Comparative Li (17)-0.02-LiBF2(Ox)-1- 100 100 Example31-2 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative Li (18)-0.02-LiBF2(Ox)-1-100 100 Example 31-3 LiN(SO2F)(POF2)-1-V4Si-0.1 Example 32-1 Li(2)-0.02- 104 104 LiN(FSO2)(POFpropynyloxy)-1-LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Example 32-2 Li (4)-0.02- 103 104LiN(FSO2)(POFpropynyloxy)-1- Li SO3F-0.2-LiPO2F2-0.2-TBB-1.5 Example32-3 Li (6)-0.02- 103 103 LiN(FSO2)(POFpropynyloxy)-1-LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Example 32-4 Li (9)-0.02- 103 102LiN(FSO2)(POFpropynyloxy)-1- LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Example 32-5Li (15)-0.02- 103 102 LiN(FSO2)(POFpropynyloxy)-1-LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Comparative(0)-LiN(FSO2)(POFpropynyloxy)-1- 100 100 Example 32-0LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Comparative(0)-LiN(FSO2)(POFpropynyloxy)-1- 100 100 Example 32-1LiSO3F-0.2-LiP02F2-0.2-TBB-1.5- VC-0.02 Comparative Li (17)-0.02- 100100 Example 32-2 LiN(FSO2)(POFpropynyloxy)-1-LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Comparative Li (18)-0.02- 100 100 Example32-3 LiN(FSO2)(POFpropynyloxy)-1- LiSO3F-0.2-LiPO2F2-0.2-TBB-1.5 Example33-1 Li (2)-0.01- 103 102 LiN(FSO2)(POFpropynyloxy)-1-LiPO2F2-0.2-DTDO-0.5-FEC-1 Example 33-2 Li (4)-0.01- 104 103LiN(FSO2)(POFpropynyloxy)-1- LiPO2F2-0.2-DTDO-0.5-FEC-1 Example 33-3 Li(6)-0.01- 103 102 LiN(FSO2)(POFpropynyloxy)-1-LiPO2F2-0.2-DTDO-0.5-FEC-1 Example 33-4 Li (9)-0.01- 104 103LiN(FSO2)(POFpropynyloxy)-1- LiPO2F2-0.2-DTDO-0.5-FEC-1 Example 33-5 Li(15)-0.01- 102 103 LiN(FSO2)(POFpropynyloxy)-1-LiPO2F2-0.2-DTDO-0.5-FEC-1 Comparative (0)-LiN(FSO2)(POFpropynyloxy)-1-100 100 Example 33-0 LiPO2F2-0.2-DTDO-0.5-FEC-1 Comparative(0)-LiN(FSO2)(POFpropynyloxy)-1- 100 100 Example 33-1LiPO2F2-0.2-DTDO-0.5-FEC-1-VC- 0.01 Comparative Li (17)-0.01- 100 100Example 33-2 LiN(FSO2)(POFpropynyloxy)-1- LiPO2F2-0.2-DTDO-0.5-FEC-1Comparative Li (18)-0.01- 100 100 Example 33-3LiN(FSO2)(POFpropynyloxy)-1- LiPO2F2-0.2-DTDO-0.5-FEC-1 *In Examples31-1 to 31-5 and Comparative Examples 31-1 to 31-3, the values were eacha relative value when the result of evaluation in Comparative Example31-0 was defined as 100. *In Examples 32-1 to 32-5 and ComparativeExamples 32-1 to 32-3, the values were each a relative value when theresult of evaluation in Comparative Example 32-0 was defined as 100. *InExamples 33-1 to 33-5 and Comparative Examples 33-1 to 33-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 33-0 was defined as 100.

Incidentally, in the tables, “LiPF2(Ox)2” means LiPF₂(C₂O₄)₂, “LiPF4(Ox)” means LiPF₄(C₂O₄), “LiBF₂(Ox)” means LiBF₂(C₂O₄), “LiBOB” meansLiB(C₂O₄)₂, “LiN(FSO2)(POFpropynyloxy)” means LiN(FSO₂)(POF(OCH₂C≡CH)),“FEC” means fluoroethylene carbonate, “PS” means 1,3-propanesultone,“DTDO” means 1,3,2-dioxathiolane 2,2-dioxide, “V4Si” meanstetravinylsilane, “TBB” means t-butylbenzene, “BP” means biphenyl, and“CHB” means cyclohexylbenzene.

Examples and Comparative Examples Having Variously Modified NegativeElectrode Bodies

Batteries having the structures in which the electrolyte solutions andthe negative electrode bodies were variously modified as shown in Tables23 to 25 were produced and were evaluated as described above.

TABLE 23 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 34-1Li (1)-1 LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Li₄Ti₅O₁₂ 110 108 Example 34-2 Li(2)-1 112 115 Example 34-3 Li (9)-1 126 113 Comparative (0) 100 100Example 34-0 Comparative (0)-VC-1 103 90 Example 34-1 Comparative Li(17)-1 107 100 Example 34-2 Comparative Li (18)-1 101 100 Example 34-3Comparative (0)-LiPO2F2-1-[1.1] 100 100 Example 35-0 Comparative(0)-LiPO2F2-1-VC-0.5-[1.1] 103 94 Example 35-1 Comparative Li(17)-0.5-LiPO2F2-1-[1.1] 105 100 Example 35-2 Comparative Li(18)-0.5-LiPO2F2-1-[1.1] 100 100 Example 35-3 Example 36-1 Li(2)-0.5-LiN(SO2F)2-3-LiPO2F2- 115 110 0.5 Example 36-2 Li(4)-0.5-LiN(SO2F)2-3-LiPO2F2- 112 115 0.5 Comparative(0)-LiN(SO2F)2-3-LiPO2F2-0.5 100 100 Example 36-0 Comparative(0)-LiN(SO2F)2-3-LiPO2F2-0.5- 102 94 Example 36-1 VC-0.5 Comparative Li(17)-0.5-LiN(SO2F)2-3- 103 100 Example 36-2 LiPO2F2-0.5 Comparative Li(18)-0.5-LiN(SO2F)2-3- 101 100 Example 36-3 LiPO2F2-0.5 *In Examples34-1 to 34-3 and Comparative Examples 34-1 to 34-3, the values were eacha relative value when the result of evaluation in Comparative Example34-0 was defined as 100. *In Comparative Examples 35-1 to 35-3, thevalues were each a relative value when the result of evaluation inComparative Example 35-0 was defined as 100. *In Examples 36-1 and 36-2and Comparative Examples 36-1 to 36-3, the values were each a relativevalue when the result of evaluation in Comparative Example 36-0 wasdefined as 100.

TABLE 24 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 37-1Li (4)-1 LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Graphite 130 135 Example 37-2 Li(9)-1 (containing 132 140 Example 37-3 Li (15)-1 silicon) 129 133Comparative (0) 100 100 Example 37-0 Comparative (0)-VC-1 102 90 Example37-1 Comparative Li (17)-1 105 99 Example 37-2 Comparative Li (18)-1 101100 Example 37-3 Example 38-1 Li (4)-0.02-LiN(SO2F)(POF2)-1 108 109Example 38-2 Li (9)-0.02-LiN(SO2F)(POF2)-1 107 110 Example 38-3 Li(15)-0.02-LiN(SO2F)(POF2)-1 106 108 Comparative (0)-LiN(SO2F)(POF2)-1100 100 Example 38-0 Comparative (0)-LiN(SO2F)(POF2)-1-VC- 100 99Example 38-1 0.02 Comparative Li (17)-0.02-LiN(SO2F)(POF2)-1 100 100Example 38-2 Comparative Li (18)-0.02-LiN(SO2F)(POF2)-1 100 100 Example38-3 Example 39-1 Li (2)-0.5-LiN(SO2F)2-3- 118 121 LiPO2F2-0.5 Example39-2 Li (9)-0.5-LiN(SO2F)2-3- 118 119 LiPO2F2-0.5 Example 39-3 Li(15)-0.5-LiN(SO2F)2-3- 119 117 LiPO2F2-0.5 Comparative(0)-LiN(SO2F)2-3-LiPO2F2-0.5 100 100 Example 39-0 Comparative(0)-LiN(SO2F)2-3-LiPO2F2-0.5- 102 92 Example 39-1 VC-0.5 Comparative Li(17)-0.5-LiN(SO2F)2-3- 104 100 Example 39-2 LiPO2F2-0.5 Comparative Li(18)-0.5-LiN(SO2F)2-3- 100 100 Example 39-3 LiPO2F2-0.5 Example 40-1 Li(4)-0.02-LiBF2(Ox)-1- 105 108 LiN(SO2F)(POF2)-1-V4Si-0.1 Example 40-2 Li(6)-0.02-LiBF2(Ox)-1- 105 107 LiN(SO2F)(POF2)-1-V4Si-0.1 Example 40-3 Li(9)-0.02-LiBF2(Ox)-1- 106 107 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative(0)-LiBF2(Ox)-1- 100 100 Example 40-0 LiN(SO2F)(POF2)-1-V4Si-0.1Comparative (0)-LiBF2(Ox)-1- 100 100 Example 40-1LiN(SO2F)(POF2)-1-V4Si-0.1- VC-0.02 Comparative Li(17)-0.02-LiBF2(Ox)-1- 100 100 Example 40-2 LiN(SO2F)(POF2)-1-V4Si-0.1Comparative Li (18)-0.02-LiBF2(Ox)-1- 100 100 Example 40-3LiN(SO2F)(POF2)-1-V4Si-0.1 *In Examples 37-1 to 37-3 and ComparativeExamples 37-1 to 37-3, the values were each a relative value when theresult of evaluation in Comparative Example 37-0 was defined as 100. *InExamples 38-1 to 38-3 and Comparative Examples 38-1 to 38-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 38-0 was defined as 100. *In Examples 39-1 to 39-3 andComparative Examples 39-1 to 39-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 39-0 was defined as100. *In Examples 40-1 to 40-3 and Comparative Examples 40-1 to 40-3,the values were each a relative value when the result of evaluation inComparative Example 40-0 was defined as 100.

TABLE 25 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 41-1Li (4)-1 LiNi_(0.6)Co_(0.2)Mn_(0.2)O₂ Hard 115 120 Example 41-2 Li (9)-1carbon 117 112 Example 41-3 Li (15)-1 119 111 Comparative (0) 100 100Example 41-0 Comparative (0)-VC-1 104 94 Example 41-1 Comparative Li(17)-1 103 100 Example 41-2 Comparative Li (18)-1 100 100 Example 41-3Example 42-1 Li (2)-0.02-LiPF4(Ox)-1.5- 104 104LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 42-2 Li(4)-0.02-LiPF4(Ox)-1.5- 104 106 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Example 42-3 Li (15)-0.02-LiPF4(Ox)-1.5- 103 104LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative (0)-LiPF4(Ox)-1.5-100 100 Example 42-0 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative(0)-LiPF4(Ox)-1.5- 100 100 Example 42-1 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5-VC-0.02 Comparative Li (17)-0.02-LiPF4(Ox)-1.5- 100 100Example 42-2 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative Li(18)-0.02-LiPF4(Ox)-1.5- 100 100 Example 42-3 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5 *In Examples 41-1 to 41-3 and Comparative Examples 41-1 to41-3, the values were each a relative value when the result ofevaluation in Comparative Example 41-0 was defined as 100. *In Examples42-1 to 42-3 and Comparative Examples 42-1 to 42-3, the values were eacha relative value when the result of evaluation in Comparative Example42-0 was defined as 100.

Incidentally, a negative electrode body whose negative electrode activematerial is Li₄Ti₅O₁₂ was produced by mixing a Li₄Ti₅O₁₂ powder (90 mass%) with PVDF (5 mass %) as a binder and acetylene black (5 mass %) as aconductive agent, further adding NMP to the resultant mixture, applyingthe resultant paste onto copper foil, and drying it. In the evaluationof the battery, the charge termination voltage was 2.7 V, and thedischarge termination voltage was 1.5 V.

A negative electrode body whose negative electrode active material isgraphite (containing silicon) was produced by mixing a graphite powder(80 mass %) with a silicon powder (10 mass %) and PVDF (10 mass %) as abinder, further adding NMP to the resultant mixture, applying theresultant paste onto copper foil, and drying it. In the evaluation ofthe battery, the charge termination voltage and the dischargetermination voltage were the same as those in Example 1-1.

A negative electrode body whose negative electrode active material ishard carbon was produced by mixing hard carbon (90 mass %) with PVDF (5mass %) as a binder and acetylene black (5 mass %) as a conductiveagent, further adding NMP to the resultant mixture, applying theresultant paste onto copper foil, and drying it. In the evaluation ofthe battery, the charge termination voltage was 4.2 V, and the dischargetermination voltage was 2.2 V.

It was confirmed that also for each of the electrode compositions usingLi₄Ti₅O₁₂, graphite (containing silicon), and hard carbon as thenegative electrode active material as described above, thehigh-temperature cycle properties and the low-temperature outputproperties can be exhibited in a well-balanced manner by using anelectrolyte solution containing the ionic compound of the presentinvention.

Accordingly, the non-aqueous electrolyte solution battery that canexhibit the high-temperature cycle properties and the low-temperatureoutput properties in a well-balanced manner was obtained regardless ofthe type of the negative electrode active material, by using theelectrolyte solution having the composition containing the ioniccompound having the specific structure of the present invention.

Examples and Comparative Examples Having Variously Modified PositiveElectrode Bodies

Batteries having the structures in which the electrolyte solution andthe positive electrode body were variously modified as shown in Tables26 to 29 were produced and were evaluated as described above.

TABLE 26 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 43-1Li (1)-1 LiCoO₂ Graphite 111 112 Example 43-2 Li (2)-1 110 118 Example43-3 Li (9)-1 122 118 Comparative (0) 100 100 Example 43-0 Comparative(0)-VC-1 107 92 Example 43-1 Comparative Li (17)-1 107 100 Example 43-2Comparative Li (18)-1 101 100 Example 43-3 Example 44-1 Li (4)-0.5-VC-1107 112 Example 44-2 Li (9)-0.5-VC-1 110 113 Example 44-3 Li(15)-0.5-VC-1 108 109 Comparative (0)-VC-1 100 100 Example 44-0Comparative (0)-VC-1.5 104 95 Example 44-1 Comparative Li (17)-0.5-VC-1104 100 Example 44-2 Comparative Li (18)-0.5-VC-1 100 100 Example 44-3*In Examples 43-1 to 43-3 and Comparative Examples 43-1 to 43-3, thevalues were each a relative value when the result of evaluation inComparative Example 43-0 was defined as 100. *In Examples 44-1 to 44-3and Comparative Examples 44-1 to 44-3, the values were each a relativevalue when the result of evaluation in Comparative Example 44-0 wasdefined as 100.

TABLE 27 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 45-1Li (2)-1 LiNi_(0.8)Co_(0.15)Al_(0.05)O₂ Graphite 112 115 Example 45-2 Li(4)-1 119 119 Example 45-3 Li (9)-1 124 116 Comparative (0) 100 100Example 45-0 Comparative (0)-VC-1 107 94 Example 45-1 Comparative Li(17)-1 107 99 Example 45-2 Comparative Li (18)-1 101 100 Example 45-3Example 46-1 Li (2)-0.02-LiPF4(Ox)-1.5- 104 103LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 46-2 Li(4)-0.02-LiPF4(Ox)-1.5- 105 106 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Example 46-3 Li (6)-0.02-LiPF4(Ox)-1.5- 102 103LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 46-4 Li(9)-0.02-LiPF4(Ox)-1.5- 103 104 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Example 46-5 Li (15)-0.02-LiPF4(Ox)-1.5- 103 105LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative (0)-LiPF4(Ox)-1.5-100 100 Example 46-0 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative(0)-LiPF4(Ox)-1.5- 100 100 Example 46-1 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5-VC-0.02 Comparative Li (17)-0.02-LiPF4(Ox)-1.5- 100 100Example 46-2 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative Li(18)-0.02-LiPF4(Ox)-1.5- 100 100 Example 46-3 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5 Example 47-1 Li (2)-0.02-LiBF2(Ox)-1- 104 104LiN(SO2F)(POF2)-1-V4Si-0.1 Example 47-2 Li (4)-0.02-LiBF2(Ox)-1- 105 107LiN(SO2F)(POF2)-1-V4Si-0.1 Example 47-3 Li (6)-0.02-LiBF2(Ox)-1- 102 103LiN(SO2F)(POF2)-1-V4Si-0.1 Example 47-4 Li (9)-0.02-LiBF2(Ox)-1- 103 105LiN(SO2F)(POF2)-1-V4Si-0.1 Example 47-5 Li (15)-0.02-LiBF2(Ox)-1- 104104 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative (0)-LiBF2(Ox)-1- 100 100Example 47-0 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative (0)-LiBF2(Ox)-1- 100100 Example 47-1 LiN(SO2F)(POF2)-1-V4Si-0.1- VC-0.02 Comparative Li(17)-0.02-LiBF2(Ox)-1- 100 100 Example 47-2 LiN(SO2F)(POF2)-1-V4Si-0.1Comparative Li (18)-0.02-LiBF2(Ox)-1- 100 100 Example 47-3LiN(SO2F)(POF2)-1-V4Si-0.1 *In Examples 45-1 to 45-3 and ComparativeExamples 45-1 to 45-3, the values were each a relative value when theresult of evaluation in Comparative Example 45-0 was defined as 100. *InExamples 46-1 to 46-5 and Comparative Examples 46-1 to 46-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 46-0 was defined as 100. *In Examples 47-1 to 47-5 andComparative Examples 47-1 to 47-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 47-0 was defined as100.

TABLE 28 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 48-1Li (2)-1 LiMn₂O₄ Graphite 111 114 Example 48-2 Li (4)-1 119 121 Example48-3 Li (9)-1 124 116 Comparative (0) 100 100 Example 48-0 Comparative(0)-VC-1 106 91 Example 48-1 Comparative Li (17)-1 107 99 Example 48-2Comparative Li (18)-1 100 100 Example 48-3 Example 49-1 Li(2)-0.2-LiBOB-1-LiPO2F2-0.5 110 109 Example 49-2 Li(4)-0.2-LiBOB-1-LiPO2F2-0.5 111 113 Example 49-3 Li(9)-0.2-LiBOB-1-LiPO2F2-0.5 111 110 Comparative (0)-LiBOB-1-LiPO2F2-0.5100 100 Example 49-0 Comparative (0)-LiBOB-1-LiPO2F2-0.5-VC- 103 96Example 49-1 0.2 Comparative Li (17)-0.2-LiBOB-1-LiPO2F2- 103 100Example 49-2 0.5 Comparative Li (18)-0.2-LiBOB-1-LiPO2F2- 100 100Example 49-3 0.5 Example 50-1 Li (2)-0.02-LiPF4(Ox)-1.5- 103 102LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Example 50-2 Li(4)-0.02-LiPF4(Ox)-1.5- 105 105 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5Example 50-3 Li (15)-0.02-LiPF4(Ox)-1.5- 103 102LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative (0)-LiPF4(Ox)-1.5-100 100 Example 50-0 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative(0)-LiPF4(Ox)-1.5- 100 100 Example 50-1 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5-VC-0.02 Comparative Li (17)-0.02-LiPF4(Ox)-1.5- 100 100Example 50-2 LiN(SO2F)(POF2)-1-LiPO2F2- 0.1-CHB-1.5 Comparative Li(18)-0.02-LiPF4(Ox)-1.5- 100 100 Example 50-3 LiN(SO2F)(POF2)-1-LiPO2F2-0.1-CHB-1.5 *In Examples 48-1 to 48-3 and Comparative Examples 48-1 to48-3, the values were each a relative value when the result ofevaluation in Comparative Example 48-0 was defined as 100. *In Examples49-1 to 49-3 and Comparative Examples 49-1 to 49-3, the values were eacha relative value when the result of evaluation in Comparative Example49-0 was defined as 100. *In Examples 50-1 to 50-3 and ComparativeExamples 50-1 to 50-3, the values were each a relative value when theresult of evaluation in Comparative Example 50-0 was defined as 100.

TABLE 29 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 51-1Li (2)-1 LiFePO₄ Graphite 112 112 Example 51-2 Li (4)-1 117 126 Example51-3 Li (9)-1 122 118 Comparative (0) 100 100 Example 51-0 Comparative(0)-VC-1 107 92 Example 51-1 Comparative Li (17)-1 107 99 Example 51-2Comparative Li (18)-1 101 100 Example 51-3 Example 52-1 Li(4)-0.02-LiBF2(Ox)-1- 105 106 LiN(SO2F)(POF2)-1-V4Si-0.1 Example 52-2 Li(9)-0.02-LiBF2(Ox)-1- 104 103 LiN(SO2F)(POF2)-1-V4Si-0.1 Example 52-3 Li(15)-0.02-LiBF2(Ox)-1- 104 103 LiN(SO2F)(POF2)-1-V4Si-0.1 Comparative(0)-LiBF2(Ox)-1- 100 100 Example 52-0 LiN(SO2F)(POF2)-1-V4Si-0.1Comparative (0)-LiBF2(Ox)-1- 100 100 Example 52-1LiN(SO2F)(POF2)-1-V4Si-0.1- VC-0.02 Comparative Li(17)-0.02-LiBF2(Ox)-1- 100 100 Example 52-2 LiN(SO2F)(POF2)-1-V4Si-0.1Comparative Li (18)-0.02-LiBF2(Ox)-1- 100 100 Example 52-3LiN(SO2F)(POF2)-1-V4Si-0.1 *In Examples 51-1 to 51-3 and ComparativeExamples 51-1 to 51-3, the values were each a relative value when theresult of evaluation in Comparative Example 51-0 was defined as 100. *InExamples 52-1 to 52-3 and Comparative Examples 52-1 to 52-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 52-0 was defined as 100.

Incidentally, a positive electrode body whose positive electrode activematerial is LiCoO₂ was produced by mixing a LiCoO₂ powder (90 mass %)with PVDF (5 mass %) as a binder and acetylene black (5 mass %) as aconductive material, further adding NMP to the resultant mixture,applying the resultant paste onto aluminum foil, and drying it. In theevaluation of the battery, the charge termination voltage was 4.2 V, andthe discharge termination voltage was 3.0 V.

A positive electrode body whose positive electrode active material isLiNi_(0.8)Co_(0.15)Al_(0.05)O₂ was produced by mixing aLiNi_(0.8)Co_(0.15)Al_(0.05)O₂ powder (90 mass %) with PVDF (5 mass %)as a binder and acetylene black (5 mass %) as a conductive material,further adding NMP to the resultant mixture, applying the resultantpaste onto aluminum foil, and drying it. In the evaluation of thebattery, the charge termination voltage was 4.2 V, and the dischargetermination voltage was 3.0 V.

A positive electrode body whose positive electrode active material isLiMn₂O₄ was produced by mixing a LiMn₂O₄ powder (90 mass %) with PVDF (5mass %) as a binder and acetylene black (5 mass %) as a conductivematerial, further adding NMP to the resultant mixture, applying theresultant paste onto aluminum foil, and drying it. In the evaluation ofthe battery, the charge termination voltage was 4.2 V, and the dischargetermination voltage was 3.0 V.

A positive electrode body whose positive electrode active material isLiFePO₄ was produced by mixing a LiFePO₄ powder coated with amorphouscarbon (90 mass %) with PVDF (5 mass %) as a binder and acetylene black(5 mass %) as a conductive material, further adding NMP to the resultantmixture, applying the resultant paste onto aluminum foil, and drying it.In the evaluation of the battery, the charge termination voltage was 4.1V, and the discharge termination voltage was 2.5 V.

Also for each of the electrode compositions using LiCoO₂,LiNi_(0.8)Co_(0.15)Al_(0.05)O₂, LiMn₂₀O₄, and LiFePO₄ as the positiveelectrode active material as described above, it was confirmed that thehigh-temperature cycle properties and the low-temperature outputproperties can be exhibited in a well-balanced manner by using theelectrolyte solution containing the ionic compound of the presentinvention.

Accordingly, the non-aqueous electrolyte solution battery that canexhibit high-temperature cycle properties and low-temperature outputproperties in a well-balanced manner was obtained regardless of the typeof the positive electrode active material by using the electrolytesolution having the composition containing the ionic compound having thespecific structure of the present invention.

Sodium Ion Battery

Example 53-1

Preparation of Electrolyte Solution

Non-aqueous electrolyte solution No. Na(2)-0.5 [Na] was prepared byusing a mixed solvent of propylene carbonate, ethylene carbonate anddiethyl carbonate at a volume ratio of 2:1:7 as a non-aqueous solventand dissolving NaPF₆ as a solute and a Na salt of Anion (2) as the ioniccompound in the solvent such that the concentration of NaPF₆ was 1.0mol/L and that the concentration of the Na salt (the content of Cl inthe ionic compound as a raw material before being dissolved in theelectrolyte solution was 20 mass ppm, and the content of hydrofluoricacid was 110 mass ppm) was 0.5 mass % based on the total amount of thenon-aqueous solvent, the solute, and the ionic compound. The abovepreparation was performed while maintaining the solution temperature at25° C. The conditions for preparing the non-aqueous electrolyte solutionare shown in Table 30.

Production of Battery

A battery was produced as in Example 1-1 except that the aboveelectrolyte solution was used, the positive electrode material wasNaNi_(0.60)Co_(0.05)Mn_(0.35)O₂, and the negative electrode material washard carbon, and the resultant battery was evaluated as in Example 1-1.Incidentally, the positive electrode body whose positive electrodeactive material is NaNi_(0.60)Co_(0.05)Mn_(0.35)O₂ was produced bymixing a NaNi_(0.60)Co_(0.05)Mn_(0.35)O₂ powder (90 mass %) with PVDF (5mass %) as a binder and acetylene black (5 mass %) as a conductivematerial, further adding NMP to the resultant mixture, applying theresultant paste onto aluminum foil, and drying it. In the evaluation ofthe battery, the charge termination voltage was 3.9 V, and the dischargetermination voltage was 1.5 V.

The results of the evaluation of the batteries as prepared are shown inTable 31. Incidentally, the values of the discharge capacity retentionrates after cycles and the high-output capacity retention rates of thebatteries shown in Table 31 are relative values when the dischargecapacity retention rate after cycles and the high-output capacityretention rate of a laminated battery produced using the electrolytesolution No. (0) [Na] described below were each defined as 100.

TABLE 30 Other solute Ionic compound Solute and additive Type of CounterConc. Conc. Conc. Electrolyte solution No. anion cation [mass %] Type[mol/L] Type [mass %] Na (2)-0.5 [Na] (2) Na+ 0.5 NaPF₆ 1 — — Na (4)-0.5[Na] (4) Na+ 0.5 NaPF₆ 1 — — Na (6)-0.5 [Na] (6) Na+ 0.5 NaPF₆ 1 — — Na(9)-0.5 [Na] (9) Na+ 0.5 NaPF₆ 1 — — Na (15)-0.5 [Na] (15)  Na+ 0.5NaPF₆ 1 — — (0) [Na] — — — NaPF₆ 1 — — (0)-VC-0.5 [Na] — — — NaPF₆ 1 VC  0.5 Na (17)-0.5 [Na] (17)  Na+ 0.5 NaPF₆ 1 — — Na (18)-0.5 [Na] (18) Na+ 0.5 NaPF₆ 1 — — Na (2)-0.5-FEC-1 [Na] (2) Na+ 0.5 NaPF₆ 1 FEC 1 Na(4)-0.5-FEC-1 [Na] (4) Na+ 0.5 NaPF₆ 1 FEC 1 Na (6)-0.5-FEC-1 [Na] (6)Na+ 0.5 NaPF₆ 1 FEC 1 Na (9)-0.5-FEC-1 [Na] (9) Na+ 0.5 NaPF₆ 1 FEC 1 Na(15)-0.5-FEC-1 [Na] (15)  Na+ 0.5 NaPF₆ 1 FEC 1 (0)-FEC-1 [Na] — — —NaPF₆ 1 FEC 1 (0)-FEC-1-VC-0.5 [Na] — — — NaPF₆ 1 FEC, VC   1, 0.5 Na(17)-0.5-FEC-1 [Na] (17)  Na+ 0.5 NaPF₆ 1 FEC 1 Na (18)-0.5-FEC-1 [Na](18)  Na+ 0.5 NaPF₆ 1 FEC 1 Na (2)-0.5-NaPF4(Ox)-2 (2) Na+ 0.5 NaPF₆ 1NaPF₄(C₂O₄) 2 [Na] Na (4)-0.5-NaPF4(Ox)-2 (4) Na+ 0.5 NaPF₆ 1NaPF₄(C₂O₄) 2 [Na] Na (6)-0.5-NaPF4(Ox)-2 (6) Na+ 0.5 NaPF₆ 1NaPF₄(C₂O₄) 2 [Na] Na (9)-0.5-NaPF4(Ox)-2 (9) Na+ 0.5 NaPF₆ 1NaPF₄(C₂O₄) 2 [Na] Na (15)-0.5-NaPF4(Ox)-2 (15)  Na+ 0.5 NaPF₆ 1NaPF₄(C₂O₄) 2 [Na] (0)-NaPF4(Ox)-2 [Na] — — — NaPF₆ 1 NaPF₄(C₂O₄) 2(0)-NaPF4(Ox)-2-VC-0.5 — — — NaPF₆ 1 NaPF₄(C₂O₄),   2, 0.5 [Na] VC Na(17)-0.5-NaPF4(Ox)-2 (17)  Na+ 0.5 NaPF₆ 1 NaPF₄(C₂O₄) 2 [Na] Na(18)-0.5-NaPF4(Ox)-2 (18)  Na+ 0.5 NaPF₆ 1 NaPF₄(C₂O₄) 2 [Na] Na(2)-0.3-NaN(SO2F)2-1 (2) Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na(4)-0.3-NaN(SO2F)2-1 (4) Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na(6)-0.3-NaN(SO2F)2-1 (6) Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na(9)-0.3-NaN(SO2F)2-1 (9) Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na(15)-0.3-NaN(SO2F)2-1 (15)  Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na](0)-NaN(SO2F)2-1 [Na] — — — NaPF₆ 1 NaN(SO₂F)₂ 1 (0)-NaN(SO2F)2-1-VC-0.3— — — NaPF₆ 1 NaN(SO₂F)₂,   1, 0.3 [Na] VC Na (17)-0.3-NaN(SO2F)2-1(17)  Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na (18)-0.3-NaN(SO2F)2-1 (18) Na+ 0.3 NaPF₆ 1 NaN(SO₂F)₂ 1 [Na] Na (2)-0.1- (2) Na+ 0.1 NaPF₆ 1NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Na] Na (4)-0.1- (4) Na+ 0.1 NaPF₆ 1NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Na] Na (6)-0.1- (6) Na+ 0.1 NaPF₆ 1NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Na] Na (9)-0.1- (9) Na+ 0.1 NaPF₆ 1NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Nal Na (15)-0.1- (15)  Na+ 0.1NaPF₆ 1 NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Na] (0)-NaN(SO2F)(POF2)-1 —— — NaPF₆ 1 NaN(SO₂F)(POF₂) 1 [Na] (0)-NaN(SO2F)(POF2)-1- — — — NaPF₆ 1NaN(SO₂F)(POF₂),   1, 0.1 VC-0.1 [Na] VC Na (17)-0.1- (17)  Na+ 0.1NaPF₆ 1 NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Nal Na (18)-0.1- (18)  Na+0.1 NaPF₆ 1 NaN(SO₂F)(POF₂) 1 NaN(SO2F)(POF2)-1 [Na] Na (2)-0.5- (2) Na+0.5 NaPF₆ 1 NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1 FEC [Na] Na(4)-0.5- (4) Na+ 0.5 NaPF₆ 1 NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1FEC [Na] Na (6)-0.5- (6) Na+ 0.5 NaPF₆ 1 NaN(SO₂F)(COF), 1, 1NaN(SO2F)(COF)-1-FEC-1 FEC [Na] Na (9)-0.5- (9) Na+ 0.5 NaPF₆ 1NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1 FEC [Na] Na (15)-0.5- (15) Na+ 0.5 NaPF₆ 1 NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1 FEC [Na](0)-NaN(SO2F)(COF)-1- — — — NaPF₆ 1 NaN(SO₂F)(COF), 1, 1 FEC-1 [Na] FEC(0)-NaN(SO2F)(COF)-1- — — — NaPF₆ 1 NaN(SO₂F)(COF), 1, 1, 0.5FEC-1-VC-0.5 [Na] FEC, VC Na (17)-0.5- (17)  Na+ 0.5 NaPF₆ 1NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1 FEC [Na] Na (18)-0.5- (18) Na+ 0.5 NaPF₆ 1 NaN(SO₂F)(COF), 1, 1 NaN(SO2F)(COF)-1-FEC-1 FEC [Na]

TABLE 31 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 53-1Na (2)-0.5 [Na] NaNi_(0.60)Co_(0.05)Mn_(0.35)O₂ Hard 116 117 Example53-2 Na (4)-0.5 [Na] carbon 127 135 Example 53-3 Na (6)-0.5 [Na] 122 113Example 53-4 Na (9)-0.5 [Na] 117 120 Example 53-5 Na (15)-0.5 [Na] 120121 Comparative (0) [Na] 100 100 Example 53-0 Comparative (0)-VC-0.5[Na] 100 90 Example 53-1 Comparative Na (17)-0.5 [Na] 103 100 Example53-2 Comparative Na (18)-0.5 [Na] 101 100 Example 53-3 Example 54-1 Na(2)-0.5-FEC-1 [Na] 112 111 Example 54-2 Na (4)-0.5-FEC-1 [Na] 125 137Example 54-3 Na (6)-0.5-FEC-1 [Na] 119 109 Example 54-4 Na (9)-0.5-FEC-1[Na] 118 121 Example 54-5 Na (15)-0.5-FEC-1 [Na] 119 120 Comparative(0)-FEC-1 [Na] 100 100 Example 54-0 Comparative (0)-FEC-1-VC-0.5 [Na]101 95 Example 54-1 Comparative Na (17)-0.5-FEC-1 [Na] 103 100 Example54-2 Comparative Na (18)-0.5-FEC-1 [Na] 102 100 Example 54-3 *InExamples 53-1 to 53-5 and Comparative Examples 53-1 to 53-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 53-0 was defined as 100. *In Examples 54-1 to 54-5 andComparative Examples 54-1 to 54-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 54-0 was defined as100.Examples and Comparative Examples Having Variously Modified ElectrolyteSolution Compositions, Negative Electrode Bodies, and Positive ElectrodeBodies

Electrolyte solutions were each prepared by the same procedure as thatin Electrolyte solution No. Na(2)-0.5 [Na] except that the types and theconcentrations of the ionic compounds and the types and theconcentrations of other solutes and additives were variously changed asshown in Table 30.

Batteries having the electrode compositions shown in Tables 31 to 33were produced using the resultant electrolyte solutions by the sameprocedure as that in Example 53-1 and were evaluated as described above.

Incidentally, the positive electrode body whose positive electrodeactive material is NaFeo_(0.4)Ni_(0.3)Mn_(0.3)O₂ was produced by mixinga NaFe_(0.4)Ni_(0.3)Mn_(0.3)O₂ powder (90 mass %) with PVDF (5 mass %)as a binder and acetylene black (5 mass %) as a conductive material,further adding NMP to the resultant mixture, applying the resultantpaste onto aluminum foil, and drying it. In the evaluation of thebattery, the charge termination voltage was 4.1 V, and the dischargetermination voltage was 2.0 V.

The positive electrode body whose positive electrode active material isNaNi_(1/3)Ti_(1/6)Mn_(1/2)O₂ was produced by mixing aNaNi_(1/3)Ti_(1/6)Mn_(1/2)O₂ powder (90 mass %) with PVDF (5 mass %) asa binder and acetylene black (5 mass %) as a conductive material,further adding NMP to the resultant mixture, applying the resultantpaste onto aluminum foil, and drying it. In the evaluation of thebattery, the charge termination voltage was 4.5 V, and the dischargetermination voltage was 1.5 V.

TABLE 32 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 55-1Na (2)-0.5-NaPF4(Ox)-2 NaFe_(0.4)Ni_(0.3)Mn_(0.3)O₂ Hard 115 110 [Na]carbon Example 55-2 Na (4)-0.5-NaPF4(Ox)-2 128 125 [Na] Example 55-3 Na(6)-0.5-NaPF4(Ox)-2 119 111 [Na] Example 55-4 Na (9)-0.5-NaPF4(Ox)-2 118113 [Na] Example 55-5 Na (15)-0.5-NaPF4(Ox)-2 120 118 [Na] Comparative(0)-NaPF4(Ox)-2 [Na] 100 100 Example 55-0 Comparative(0)-NaPF4(Ox)-2-VC-0.5 101 93 Example 55-1 [Na] Comparative Na(17)-0.5-NaPF4(Ox)-2 104 100 Example 55-2 [Na] Comparative Na(18)-0.5-NaPF4(Ox)-2 101 100 Example 55-3 [Na] Example 56-1 Na(2)-0.3-NaN(SO2F)2-1 117 116 [Na] Example 56-2 Na (4)-0.3-NaN(SO2F)2-1122 135 [Na] Example 56-3 Na (6)-0.3-NaN(SO2F)2-1 117 111 [Na] Example56-4 Na (9)-0.3-NaN(SO2F)2-1 118 117 [Na] Example 56-5 Na(15)-0.3-NaN(SO2F)2-1 119 120 [Na] Comparative (0)-NaN(SO2F)2-1 [Na] 100100 Example 56-0 Comparative (0)-NaN(SO2F)2-1-VC-0.3 100 97 Example 56-1[Na] Comparative Na (17)-0.3-NaN(SO2F)2-1 104 100 Example 56-2 [Na]Comparative Na (18)-0.3-NaN(SO2F)2-1 101 100 Example 56-3 [Na] *InExamples 55-1 to 55-5 and Comparative Examples 55-1 to 55-3, the valueswere each a relative value when the result of evaluation in ComparativeExample 55-0 was defined as 100. *In Examples 56-1 to 56-5 andComparative Examples 56-1 to 56-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 56-0 was defined as100.

TABLE 33 Discharge capacity High-output Positive Negative retentioncapacity electrode electrode rate after retention Electrolyte solutionactive active cycles* rate* No. material material [%] [%] Example 57-1Na (2)-0.1- NaNi_(1/3)Ti_(1/6)Mn_(1/2)O₂ Hard 109 108 NaN(SO2F)(POF2)-1[Na] carbon Example 57-2 Na (4)-0.1- 116 119 NaN(SO2F)(POF2)-1 [Na]Example 57-3 Na (6)-0.1- 110 107 NaN(SO2F)(POF2)-1 [Na] Example 57-4 Na(9)-0.1- 116 117 NaN(SO2F)(POF2)-1 [Na] Example 57-5 Na (15)-0.1- 111115 NaN(SO2F)(POF2)-1 [Na] Comparative (0)-NaN(SO2F)(POF2)-1 100 100Example 57-0 [Na] Comparative (0)-NaN(SO2F)(POF2)-1- 101 98 Example 57-1VC-0.1 [Na] Comparative Na (17)-0.1- 102 100 Example 57-2NaN(SO2F)(POF2)-1 [Na] Comparative Na (18)-0.1- 101 100 Example 57-3NaN(SO2F)(POF2)-1 [Na] Example 58-1 Na (2)-0.5- 113 114NaN(SO2F)(COF)-1-FEC-1 [Na] Example 58-2 Na (4)-0.5- 121 120NaN(SO2F)(COF)-1-FEC-1 [Na] Example 58-3 Na (6)-0.5- 114 115NaN(SO2F)(COF)-1-FEC-1 [Na] Example 58-4 Na (9)-0.5- 120 117NaN(SO2F)(COF)-1-FEC-1 [Na] Example 58-5 Na (15)-0.5- 121 123NaN(SO2F)(COF)-1-FEC-1 [Na] Comparative (0)-NaN(SO2F)(COF)-1- 100 100Example 58-0 FEC-1 [Na] Comparative (0)-NaN(SO2F)(COF)-1- 100 95 Example58-1 FEC-1-VC-0.5 [Na] Comparative Na (17)-0.5- 104 99 Example 58-2NaN(SO2F)(COF)-1-FEC-1 [Na] Comparative Na (18)-0.5- 101 100 Example58-3 NaN(SO2F)(COF)-1-FEC-1 [Na] *In Examples 57-1 to 57-5 andComparative Examples 57-1 to 57-3, the values were each a relative valuewhen the result of evaluation in Comparative Example 57-0 was defined as100. *In Examples 58-1 to 58-5 and Comparative Examples 58-1 to 58-3,the values were each a relative value when the result of evaluation inComparative Example 58-0 was defined as 100.

It was confirmed from the results shown in Tables 31 to 33 that also forthe sodium ion batteries, similarly, the high-temperature cycleproperties and the low-temperature output properties can be exhibited ina well-balanced manner regardless of the types of the negative electrodeactive materials and the positive electrode active materials by usingthe electrolyte solutions containing the ionic compounds of the presentinvention.

What is claimed is:
 1. An additive for a non-aqueous electrolytesolution represented by formula [1]:

wherein in formula [1], the anion is selected from the group consistingof:

M^(p+) is a proton, a metal cation, or an onium cation; and p is acation valence.
 2. The additive for a non-aqueous electrolyte solutionaccording to claim 1, wherein M^(p+) is at least one cation selectedfrom the group consisting of a proton, a lithium ion, a sodium ion, apotassium ion, a tetraalkylammonium ion, and a tetraalkylphosphoniumion.
 3. A non-aqueous electrolyte solution comprising a non-aqueoussolvent, a solute, and the additive for a non-aqueous electrolytesolution according to claim
 1. 4. The non-aqueous electrolyte solutionaccording to claim 3, wherein a content of the additive for anon-aqueous electrolyte solution is within a range of 0.005 to 5.0 mass% based on the total amount of the non-aqueous solvent, the solute, andthe additive for a non-aqueous electrolyte solution.
 5. The non-aqueouselectrolyte solution according to claim 3, wherein the solute is atleast one selected from the group consisting of LiPF₆, LiBF₄,LiPF₂(C₂O₄)₂, LiPF₄(C₂O₄)₂, LiP(C₂O₄)₃, LiBF₂(C₂O₄), LiB(C₂O₄)₂,LiPO₂F₂, LiN(POF₂)₂, LiN(FSO₂)(POF₂), LiN(FSO₂)(POF(OCH₂C≡CH)),LiN(FSO₂)₂, LiN(CF₃SO₂)₂, LiN(CF₃SO₂)(FSO₂), LiSO₃F, NaPF₆, NaBF₄,NaPF₂(C₂O₄)₂, NaPF₄(C₂O₄), NaP(C₂O₄)₃, NaBF₂(C₂O₄), NaB(C₂O₄)₂, NaPO₂F₂,NaN(POF₂)₂, NaN(FSO₂)(POF₂), NaN(FSO₂)(POF(OCH₂C≡CH)), NaN(FSO₂)₂,NaN(FSO₂)(FCO), NaN(CF₃SO₂)₂, NaN(CF₃SO₂)(FSO₂), and NaSO₃F.
 6. Thenon-aqueous electrolyte solution according to claim 3, furthercomprising at least one selected from the group consisting of vinylenecarbonate, fluoroethylene carbonate, 1,3,2-dioxathiolane 2,2-dioxide,tetravinylsilane, and 1,3-propanesultone.
 7. The non-aqueous electrolytesolution according to claim 3, wherein the non-aqueous solvent is atleast one selected from the group consisting of a cyclic carbonate, achain carbonate, a cyclic ester, a chain ester, a cyclic ether, a chainether, a sulfone compound, a sulfoxide compound, and an ionic liquid. 8.A non-aqueous electrolyte solution battery at least comprising apositive electrode, a negative electrode, and the non-aqueouselectrolyte solution according to claim 3.